Iron species determination by task-specific ionic liquid-based in situ solvent formation dispersive liquid-liquid microextraction combined with flame atomic absorption spectrometry.

PubMed

Sadeghi, Susan; Ashoori, Vahid

2017-10-01

The task-specific ionic liquid (TSIL) of 1-ethyl-3-methylimidazolium bromide functionalized with 8-hydroxyquinoline was used as a chelating agent and extracting solvent for dispersive liquid-liquid microextraction and subsequent determination of Fe(III) by flame atomic absorption spectrometry. The in situ solvent formation of TSIL using KPF 6 provided the desired water-immiscible ionic liquid. The total Fe concentration could be determined after pre-oxidation of Fe(II) to Fe(III). Various factors affecting the proposed extraction procedure were optimized. The proposed analytical conditions were: sample pH 5, TSIL amount 0.3% (w/v), KPF 6 amount 0.15% (w/v), anti-sticking 0.1% (w/v) and salt concentration 5% (w/v). Under optimal conditions, the linear dynamic ranges for Fe(III) and total Fe were 20-80 and 20-110 ng mL -1 , respectively, with a detection limit of 6.9 ng mL -1 for Fe(III) and relative standard deviation of 2.2%. The proposed method was successfully applied to the determination of trace Fe(III) in water (underground, tap, refined water and artificial sea water) and beverage (apple, tomato, and tea) samples. The developed method offers advantages such as simplicity, ease of operation, and extraction of Fe(III) from aqueous solutions without the use of organic solvent. It was successfully applied for iron speciation in different real samples. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Varicella Zoster Virus Promoter Sequences

DTIC Science & Technology

1994-01-01

Fragments from each of the recombinant plasmids were excised to determine the optimal sequences used for promoter function. The ExonucleaseIII/ Mung ...activation o f these two herpesvirus l ate promoters by vzv is str i kingly similar . 4 . Definition of the functional promo ter for the early/late ILl

[EFFICACY OF STANDARD TWO-YEAR COMPREHENSIVE THERAPY TO ACHIEVE TARGET BLOOD PRESSURE AND REGRESSION DEGREES OF REMODELING OF THE LEFT VENTRICULAR HYPERTROPHY IN PATIENTS AFTER ACUTE MYOCARDIAL INFARCTION WITH COMORBID HYPERTENSION].

PubMed

Denesiuk, E V

2015-01-01

The study involved 23 men after acute myocardial infarction (AMI) with comorbid arterial hypertension (AH). Mean age of patients was 56.7 years. Recurrent myocardial infarction was determined in 38.4%, cardiac failure I-III functional classes--100% of the cases. All patients underwent clinical examination, electrocardiography and echocardiography, blood lipid profile. Standard comprehensive treatment for two years included an perindopril 5-10 mg/day, beta-blocker bisoprolol--5-10 mg/day, antisclerotic drug atorvastatin--20 mg/day and aspirin--75 mg/day. The patients after treatment was determined by a gradual increase towards the target of AT at 3, 6 and 12 to 24 months. Concentric left ventricular hypertrophy (LVH) before treatment was determined in 47.8%, eccentric--in 52.2% of patients. In the study of degrees of LVH I (initial) the extent to treatment was determined by 4.3%, II (moderate)--26.1%, III (large)--at 69.6%, indicating the development of cardiac remodeling. After the treatment was determined by marked reduction III (large) degree and transfer it in the II (moderate) and I (small) degree of left ventricular hypertrophy due to more or less pronounced changes remodeling left ventricular. The obtained data allow a more detailed and adequately assess the structural and functional outcome variables and determine the regression of myocardial hypertrophy in the background to achieve target blood pressure, which is important in practical cardiology.

The Populus class III HD ZIP, popREVOLUTA, influences cambium initiation and patterning of woody stems.

PubMed

Robischon, Marcel; Du, Juan; Miura, Eriko; Groover, Andrew

2011-03-01

The secondary growth of a woody stem requires the formation of a vascular cambium at an appropriate position and proper patterning of the vascular tissues derived from the cambium. Class III homeodomain-leucine zipper (HD ZIP) transcription factors have been implicated in polarity determination and patterning in lateral organs and primary vascular tissues and in the initiation and function of shoot apical meristems. We report here the functional characterization of a Populus class III HD ZIP gene, popREVOLUTA (PRE), that demonstrates another role for class III HD ZIPs in regulating the development of cambia and secondary vascular tissues. PRE is orthologous to Arabidopsis (Arabidopsis thaliana) REVOLUTA and is expressed in both the shoot apical meristem and in the cambial zone and secondary vascular tissues. Transgenic Populus expressing a microRNA-resistant form of PRE presents unstable phenotypic abnormalities affecting both primary and secondary growth. Surprisingly, phenotypic changes include abnormal formation of cambia within cortical parenchyma that can produce secondary vascular tissues in reverse polarity. Genes misexpressed in PRE mutants include transcription factors and auxin-related genes previously implicated in class III HD ZIP functions during primary growth. Together, these results suggest that PRE plays a fundamental role in the initiation of the cambium and in regulating the patterning of secondary vascular tissues.

Radio Frequency Controlled Stimulation of Intracellular Gold or Silver Nanoparticle Conjugates for Use as Potential Sensors or Modulators of Biological Function

DTIC Science & Technology

2010-09-01

SIGNED//___________ DAVID R. MATTIE , PhD, DR-III...RESPONSIBLE PERSON David R. Mattie a. REPORT U b. ABSTRACT U c. THIS PAGE U SAR 72 19b. TELEPHONE...used as a cellular model to determine the interaction of NPs with human skin. HaCaT cells were donated generously by Dr. James F. Dillman III, of the

Gamma-resonance investigation of the kinetics of the reduction of (. cap alpha. -benzil dioximato-1)(. cap alpha. -benzil dioximato-2)di(pyridine)iron(III)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Turte, K.I.; Bulgak, I.I.; Stukan, R.A.

1986-07-01

(..cap alpha..-Benzil dioximato-1)(..cap alpha..-benzil dioximato-2)di(pyridine)iron(III) in the form of the diacetone solvate (II) is spontaneously converted at room temperature into (..cap alpha..-benzil dioximato-1)(..cap alpha..-benzil dioximato-2)di(pyridine)iron(II) (III). The quantitative composition of a sample containing complexes II and III has been determined as a function of the temperature and the time by gamma-resonance spectroscopy, which made it possible to investigate the kinetics of this reaction. The changes obtained in the percentage of complex II in the sample as a function of time at a given temperature was treated with the use of the Kolmogorov-Erofeev equation for a topochemical reaction of the typemore » A/sub s/ ..-->.. B/sub s/ + C/sub g/. The rate constants of the reaction at various temperatures and the activation energy *E have been determined. In the temperature range from 293 to 304/sup 0/K *E = 25.6 kcal/mole. The possibilities of gamma-resonance spectroscopy in the investigation of topochemical reactions associated with changes in the oxidation state of iron ions have been demonstrated.« less

Determination of L-AP4-bound human mGlu8 receptor amino terminal domain structure and the molecular basis for L-AP4’s group III mGlu receptor functional potency and selectivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schkeryantz, Jeffery M.; Chen, Qi; Ho, Joseph D.

Here, L-2-Amino-4-phosphonobutyric acid (L-AP4) is a known potent and selective agonist for the Group III mGlu receptors. However, it does not show any selectivity among the individual group III mGlu subtypes. In order to understand the molecular basis for this group selectivity, we solved the first human mGlu8 amino terminal domain (ATD) crystal structures in complex with L-glu and L-AP4. In comparison with other published L-glu-bound mGlu ATD structures, we have observed L-glu binds in a significantly different manner in mGlu1. Furthermore, these new structures provided evidence that both the electronic and steric nature of the distal phosphate of L-AP4more » contribute to its exquisite Group III functional agonist potency and selectivity.« less

Influence of geogenic factors on microbial communities in metallogenic Australian soils

PubMed Central

Reith, Frank; Brugger, Joel; Zammit, Carla M; Gregg, Adrienne L; Goldfarb, Katherine C; Andersen, Gary L; DeSantis, Todd Z; Piceno, Yvette M; Brodie, Eoin L; Lu, Zhenmei; He, Zhili; Zhou, Jizhong; Wakelin, Steven A

2012-01-01

Links between microbial community assemblages and geogenic factors were assessed in 187 soil samples collected from four metal-rich provinces across Australia. Field-fresh soils and soils incubated with soluble Au(III) complexes were analysed using three-domain multiplex-terminal restriction fragment length polymorphism, and phylogenetic (PhyloChip) and functional (GeoChip) microarrays. Geogenic factors of soils were determined using lithological-, geomorphological- and soil-mapping combined with analyses of 51 geochemical parameters. Microbial communities differed significantly between landforms, soil horizons, lithologies and also with the occurrence of underlying Au deposits. The strongest responses to these factors, and to amendment with soluble Au(III) complexes, was observed in bacterial communities. PhyloChip analyses revealed a greater abundance and diversity of Alphaproteobacteria (especially Sphingomonas spp.), and Firmicutes (Bacillus spp.) in Au-containing and Au(III)-amended soils. Analyses of potential function (GeoChip) revealed higher abundances of metal-resistance genes in metal-rich soils. For example, genes that hybridised with metal-resistance genes copA, chrA and czcA of a prevalent aurophillic bacterium, Cupriavidus metallidurans CH34, occurred only in auriferous soils. These data help establish key links between geogenic factors and the phylogeny and function within soil microbial communities. In particular, the landform, which is a crucial factor in determining soil geochemistry, strongly affected microbial community structures. PMID:22673626

Influence of geogenic factors on microbial communities in metallogenic Australian soils.

PubMed

Reith, Frank; Brugger, Joel; Zammit, Carla M; Gregg, Adrienne L; Goldfarb, Katherine C; Andersen, Gary L; DeSantis, Todd Z; Piceno, Yvette M; Brodie, Eoin L; Lu, Zhenmei; He, Zhili; Zhou, Jizhong; Wakelin, Steven A

2012-11-01

Links between microbial community assemblages and geogenic factors were assessed in 187 soil samples collected from four metal-rich provinces across Australia. Field-fresh soils and soils incubated with soluble Au(III) complexes were analysed using three-domain multiplex-terminal restriction fragment length polymorphism, and phylogenetic (PhyloChip) and functional (GeoChip) microarrays. Geogenic factors of soils were determined using lithological-, geomorphological- and soil-mapping combined with analyses of 51 geochemical parameters. Microbial communities differed significantly between landforms, soil horizons, lithologies and also with the occurrence of underlying Au deposits. The strongest responses to these factors, and to amendment with soluble Au(III) complexes, was observed in bacterial communities. PhyloChip analyses revealed a greater abundance and diversity of Alphaproteobacteria (especially Sphingomonas spp.), and Firmicutes (Bacillus spp.) in Au-containing and Au(III)-amended soils. Analyses of potential function (GeoChip) revealed higher abundances of metal-resistance genes in metal-rich soils. For example, genes that hybridised with metal-resistance genes copA, chrA and czcA of a prevalent aurophillic bacterium, Cupriavidus metallidurans CH34, occurred only in auriferous soils. These data help establish key links between geogenic factors and the phylogeny and function within soil microbial communities. In particular, the landform, which is a crucial factor in determining soil geochemistry, strongly affected microbial community structures.

Cytotoxicity of Manganese (III) Complex in Human Breast Adenocarcinoma Cell Line Is Mediated by the Generation of Reactive Oxygen Species Followed by Mitochondrial Damage.

PubMed

Al-Anbaky, Qudes; Al-Karakooly, Zeiyad; Kilaparty, Surya P; Agrawal, Megha; Albkuri, Yahya M; RanguMagar, Ambar B; Ghosh, Anindya; Ali, Nawab

2016-11-01

Manganese (Mn) complexes are widely studied because of their important catalytic properties in synthetic and biochemical reactions. A Mn (III) complex of an amidoamine ligand was synthesized using a tetradentate amidoamine ligand. In this study, the Mn (III) complex was evaluated for its biological activity by measuring its cytotoxicity in human breast adenocarcinoma cell line (MCF-7). Cytotoxic effects of the Mn (III) complex were determined using established biomarkers in an attempt to delineate the mechanism of action and the utility of the complex as a potential anticancer drug. The Mn (III) complex induces cell death in a dose- and time-dependent manner as shown by microculture tetrazolium assay, a measure of cytotoxic cell death. Our results demonstrated that cytotoxic effects were significantly increased at higher concentrations of Mn (III) complex and with longer time of treatment. The IC 50 (Inhibitor concentration that results in 50% cell death) value of Mn (III) complex in MCF-7 cells was determined to be 2.5 mmol/L for 24 hours of treatment. In additional experiments, we determined the Mn (III) complex-mediated cell death was due to both apoptotic and nonspecific necrotic cell death mechanisms. This was assessed by ethidium bromide/acridine orange staining and flow cytometry techniques. The Mn (III) complex produced reactive oxygen species (ROS) triggering the expression of manganese superoxide dismutase 1 and ultimately damaging the mitochondrial function as is evident by a decline in mitochondrial membrane potential. Treatment of the cells with free radical scavenger, N, N-dimethylthiourea decreased Mn (III) complex-mediated generation of ROS and attenuated apoptosis. Together, these results suggest that the Mn (III) complex-mediated MCF-7 cell death utilizes combined mechanism involving apoptosis and necrosis perhaps due to the generation of ROS. © The Author(s) 2016.

Structural and functional characterization of two unusual endonuclease III enzymes from Deinococcus radiodurans.

PubMed

Sarre, Aili; Ökvist, Mats; Klar, Tobias; Hall, David R; Smalås, Arne O; McSweeney, Sean; Timmins, Joanna; Moe, Elin

2015-08-01

While most bacteria possess a single gene encoding the bifunctional DNA glycosylase Endonuclease III (EndoIII) in their genomes, Deinococcus radiodurans possesses three: DR2438 (DrEndoIII1), DR0289 (DrEndoIII2) and DR0982 (DrEndoIII3). Here we have determined the crystal structures of DrEndoIII1 and an N-terminally truncated form of DrEndoIII3 (DrEndoIII3Δ76). We have also generated a homology model of DrEndoIII2 and measured activity of the three enzymes. All three structures consist of two all α-helical domains, one of which exhibits a [4Fe-4S] cluster and the other a HhH-motif, separated by a DNA binding cleft, similar to previously determined structures of endonuclease III from Escherichia coli and Geobacillus stearothermophilus. However, both DrEndoIII1 and DrEndoIII3 possess an extended HhH motif with extra helical features and an altered electrostatic surface potential. In addition, the DNA binding cleft of DrEndoIII3 seems to be less accessible for DNA interactions, while in DrEndoIII1 it seems to be more open. Analysis of the enzyme activities shows that DrEndoIII2 is most similar to the previously studied enzymes, while DrEndoIII1 seems to be more distant with a weaker activity towards substrate DNA containing either thymine glycol or an abasic site. DrEndoIII3 is the most distantly related enzyme and displays no detectable activity towards these substrates even though the suggested catalytic residues are conserved. Based on a comparative structural analysis, we suggest that the altered surface potential, shape of the substrate-binding pockets and specific amino acid substitutions close to the active site and in the DNA interacting loops may underlie the unexpected differences in activity. Copyright © 2015 Elsevier Inc. All rights reserved.

Kinetics of oxidation of an organic amine with a Cr(V) salen complex in homogeneous aqueous solution and on the surface of mesoporous silica

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szajna-Fuller, Ewa; Huang, Yulin; Rapp, Jennifer L.

2009-03-09

A comparative study of catalytic activity under homogeneous and heterogeneous conditions was carried out using the (salen)Cr{sup III}-catalyzed oxidation of tetramethylbenzidine (TMB) with iodosobenzene as a model reaction. Amine-functionalized mesoporous silica nanoparticles (MSN) were synthesized in a co-condensation reaction and functionalized with salen via a covalent Si-C bond. A Cr(III) complex of this supported ligand, MSN-(salen)Cr{sup III}, was prepared and characterized. Data from powder XRD, BET isotherms and BJH pore size distribution all showed that MSN-(salen)Cr{sup III} still had the typical MSN high surface area, narrow pore size distribution, and ordered hexagonal pore structure, which were further confirmed by transmissionmore » electron microscopy (TEM) images. {sup 13}C and {sup 29}Si solid-state NMR data provided structural information about the catalyst and verified successful functionalization of the salen ligand and coordination to Cr(III). No unreacted salen or Cr(III) were observed. The loadings of salen and salen-Cr{sup III} complex were determined via TGA and EDX, respectively. Both measurements indicated that approximately 0.5 mmol/g of catalyst was loaded on the surface of MSN. The oxidation of TMB with iodosobenzene using MSN-(salen)Cr{sup III} as a heterogeneous catalyst exhibited both similarities and differences with the analogous homogeneous reaction using (salen)Cr{sup III}(H{sub 2}O){sup +} as a catalyst in aqueous acetonitrile. In the presence of 0.10 M HClO{sub 4}, the two catalytic reactions proceeded at similar rates and generated the doubly oxidized product TMB{sup 2+}. In the absence of acid, the radical cation TMB{sup +} was produced. The kinetics of the heterogeneous reaction in the absence of added acid responded to concentrations of all three reagents, i.e. (salen)Cr{sup III}, TMB, and PhIO.« less

Optical and relaxometric properties of monometallic (Eu(III), Tb(III), Gd(III)) and heterobimetallic (Re(I)/Gd(III)) systems based on a functionalized bipyridine-containing acyclic ligand.

PubMed

Leygue, Nadine; Boulay, Alexandre; Galaup, Chantal; Benoist, Eric; Laurent, Sophie; Vander Elst, Luce; Mestre-Voegtlé, Béatrice; Picard, Claude

2016-05-17

A series of lanthanide complexes of [LnL(H2O)](2-) composition where Ln = Eu(III), Tb(III) or Gd(III) has been studied for determining their photophysical and relaxometric properties in aqueous solution. The bifunctional ligand L (H5BPMNTA) is an acyclic chelator based on a central functionalized 2,2'-bipyridine core and two iminodiacetate coordinating arms. The mono-aqua Eu(III) and Tb(III) complexes display attractive spectroscopic properties with an excitation wavelength at 316 nm, similar excited state lifetimes and overall quantum yields (in the ranges 0.5-0.6 ms and 10-13%, respectively) in Tris buffer (pH 7.4). The proton longitudinal relaxivity, r1, of the Gd(III) complex is 4.4 mM(-1) s(-1) at 20 MHz and 310 K, which is comparable to that of the clinically used Gd-DTPA (Magnevist®). Interestingly, the water exchange rate between the coordination site and the bulk solvent is very fast (Kex = 2.6 × 10(8) s(-1) at 310 K). The ability of the complex to bind non-covalently to human serum albumin (HSA) was also examined by relaxometric measurements. We also report the synthesis and properties of a bimetallic complex based on Gd-BPMNTA and Re(I)(bpy)(CO)3 components. In this system, the Re core exhibits interesting photophysical properties (λem = 588 nm, Φ = 1.4%) and the Gd-BPMNTA core displays improved relaxivity (r1 = 6.6 mM(-1) s(-1) at 20 MHz and 310 K), due to an increase of the rotational correlation time. Besides these appealing optical and relaxometric properties, the presence of a reactive function on the structure proposes this potential dual imaging probe for conjugation to biomolecules or nanomaterials.

ALMA WILL DETERMINE THE SPECTROSCOPIC REDSHIFT z > 8 WITH FIR [O III] EMISSION LINES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Inoue, A. K.; Shimizu, I.; Tamura, Y.

We investigate the potential use of nebular emission lines in the rest-frame far-infrared (FIR) for determining spectroscopic redshift of z > 8 galaxies with the Atacama Large Millimeter/submillimeter Array (ALMA). After making a line emissivity model as a function of metallicity, especially for the [O III] 88 μm line which is likely to be the strongest FIR line from H II regions, we predict the line fluxes from high-z galaxies based on a cosmological hydrodynamics simulation of galaxy formation. Since the metallicity of galaxies reaches at ∼0.2 Z {sub ☉} even at z > 8 in our simulation, we expectmore » the [O III] 88 μm line as strong as 1.3 mJy for 27 AB objects, which is detectable at a high significance by <1 hr integration with ALMA. Therefore, the [O III] 88 μm line would be the best tool to confirm the spectroscopic redshifts beyond z = 8.« less

Mechanism study of humic acid functional groups for Cr(VI) retention: Two-dimensional FTIR and 13C CP/MAS NMR correlation spectroscopic analysis.

PubMed

Zhang, Jia; Chen, Linpeng; Yin, Huilin; Jin, Song; Liu, Fei; Chen, Honghan

2017-06-01

Undissolved humic acid (HA) is known to substantially effect the migration and transformation of hexavalent chromium [Cr(VI)] in soils. The mechanisms of Cr(VI) retention in soils by undissolved HA have been reported; however, past studies are inconclusive about the types of HA functional groups that are involved in Cr(VI) retention and the retention mechanisms. Utilizing a two-dimensional correlation spectroscopy (2DCOS) analysis for FTIR and 13 C CP/MAS NMR, this study investigated the variations of HA function groups and molecular structures after reactions with aqueous Cr(VI) under different pH conditions. Based on the changing sequence of functional groups interpreted from the 2DCOS results, a four-step mechanism for Cr(VI) retention was determined as follows: (1) electrostatic adsorption of Cr(VI) to HA surface, (2) complexation of adsorbed Cr(VI) by carboxyl and ester, (3) reduction of complexed Cr(VI) to Cr(III) by phenol and polysaccharide, and (4) complexation of reduced Cr(III) by carboxylic groups. These functional groups that are involved in Cr(VI) retention were determined to occur in aromatic domains. Copyright © 2017 Elsevier Ltd. All rights reserved.

Electrochemical Sensor Based on Rh(III) Ion-Imprinted Polymer as a New Modifying Agent for Rhodium Determination.

PubMed

Bai, Huiping; Xiong, Caiyun; Wang, Chunqiong; Liu, Peng; Dong, Su; Cao, Qiue

2018-05-01

A rhodium (III) ion carbon paste electrode (CPE) based on an ion imprinted polymer (IIP) as a new modifying agent has been prepared and studied. Rh(III) ion imprinted polymer was synthesized by copolymerization of acrylamide-Rh(III) complex and ethylene glycol dimethacrylate according to the precipitation polymerization. Acrylamide acted as both functional monomer and complexing agent to create selective coordination sites in a cross-linked polymer. The ion imprinted carbon paste electrode (IIP-CPE) was prepared by mixing rhodium IIP-nanoparticles and graphite powder in n-eicosane as an adhesive and then embedding them in a Teflon tube. Amperometric i-t curve method was applied as the determination technique. Several parameters, including the functional monomer, molar ratio of template, monomer and cross-linking agent, the amounts of IIP, the applied potential, the buffer solution and pH have been studied. According to the results, IIP-CPE showed a considerably higher response in comparison with the electrode embedded with non-imprinted polymer (NIP), indicating the formation of suitable recognition sites in the IIP structure during the polymerization stage. The introduced electrode showed a linear range of 1.00×10-8~3.0×10-5 mol·L-1 and detection limit of 6.0 nmol L-1 (S/N = 3). The IIP-CPE was successfully applied for the trace rhodium determination in catalyst and plant samples with RSD of less than 3.3% (n = 5) and recoveries in the range of 95.5~102.5%.

Mitochondrial function in skeletal muscle of patients with protracted critical illness and ICU-acquired weakness.

PubMed

Jiroutková, Kateřina; Krajčová, Adéla; Ziak, Jakub; Fric, Michal; Waldauf, Petr; Džupa, Valér; Gojda, Jan; Němcova-Fürstová, Vlasta; Kovář, Jan; Elkalaf, Moustafa; Trnka, Jan; Duška, František

2015-12-24

Mitochondrial damage occurs in the acute phase of critical illness, followed by activation of mitochondrial biogenesis in survivors. It has been hypothesized that bioenergetics failure of skeletal muscle may contribute to the development of ICU-acquired weakness. The aim of the present study was to determine whether mitochondrial dysfunction persists until protracted phase of critical illness. In this single-centre controlled-cohort ex vivo proof-of-concept pilot study, we obtained vastus lateralis biopsies from ventilated patients with ICU-acquired weakness (n = 8) and from age and sex-matched metabolically healthy controls (n = 8). Mitochondrial functional indices were measured in cytosolic context by high-resolution respirometry in tissue homogenates, activities of respiratory complexes by spectrophotometry and individual functional capacities were correlated with concentrations of electron transport chain key subunits from respiratory complexes II, III, IV and V measured by western blot. The ability of aerobic ATP synthesis (OXPHOS) was reduced to ~54% in ICU patients (p<0.01), in correlation with the depletion of complexes III (~38% of control, p = 0.02) and IV (~26% of controls, p<0.01) and without signs of mitochondrial uncoupling. When mitochondrial functional indices were adjusted to citrate synthase activity, OXPHOS and the activity of complexes I and IV were not different, whilst the activities of complexes II and III were increased in ICU patients 3-fold (p<0.01) respectively 2-fold (p<0.01). Compared to healthy controls, in ICU patients we have demonstrated a ~50% reduction of the ability of skeletal muscle to synthetize ATP in mitochondria. We found a depletion of complex III and IV concentrations and relative increases in functional capacities of complex II and glycerol-3-phosphate dehydrogenase/complex III.

A Novel Mechanism of Regulating the ATPase VPS4 by Its Cofactor LIP5 and the Endosomal Sorting Complex Required for Transport (ESCRT)-III Protein CHMP5

DOE PAGES

Vild, Cody J.; Li, Yan; Guo, Emily Z.; ...

2015-01-30

Disassembly of the endosomal sorting complex required for transport (ESCRT) machinery from biological membranes is a critical final step in cellular processes that require the ESCRT function. This reaction is catalyzed by VPS4, an AAA-ATPase whose activity is tightly regulated by a host of proteins, including LIP5 and the ESCRT-III proteins. In this paper, we present structural and functional analyses of molecular interactions between human VPS4, LIP5, and the ESCRT-III proteins. The N-terminal domain of LIP5 (LIP5NTD) is required for LIP5-mediated stimulation of VPS4, and the ESCRT-III protein CHMP5 strongly inhibits the stimulation. Both of these observations are distinct frommore » what was previously described for homologous yeast proteins. The crystal structure of LIP5NTD in complex with the MIT (microtubule-interacting and transport)-interacting motifs of CHMP5 and a second ESCRT-III protein, CHMP1B, was determined at 1 Å resolution. It reveals an ESCRT-III binding induced moderate conformational change in LIP5NTD, which results from insertion of a conserved CHMP5 tyrosine residue (Tyr 182) at the core of LIP5NTD structure. Finally, mutation of Tyr 182 partially relieves the inhibition displayed by CHMP5. Together, these results suggest a novel mechanism of VPS4 regulation in metazoans, where CHMP5 functions as a negative allosteric switch to control LIP5-mediated stimulation of VPS4.« less

Prepubertal exposure to arsenic(III) suppresses circulating insulin-like growth factor-1 (IGF-1) delaying sexual maturation in female rats.

PubMed

Reilly, Michael P; Saca, James C; Hamilton, Alina; Solano, Rene F; Rivera, Jesse R; Whitehouse-Innis, Wendy; Parsons, Jason G; Dearth, Robert K

2014-04-01

Arsenic (As) is a prevalent environmental toxin readily accessible for human consumption and has been identified as an endocrine disruptor. However, it is not known what impact As has on female sexual maturation. Therefore, in the present study, we investigated the effects of prepubertal exposure on mammary gland development and pubertal onset in female rats. Results showed that prepubertal exposure to 10 mg/kg of arsenite (As(III)) delayed vaginal opening (VO) and prepubertal mammary gland maturation. We determined that As accumulates in the liver, disrupts hepatocyte function and suppresses serum levels of the puberty related hormone insulin-like growth factor 1 (IGF-1) in prepubertal animals. Overall, this is the first study to show that prepubertal exposure to As(III) acts peripherally to suppress circulating levels of IGF-1 resulting in delayed sexual maturation. Furthermore, this study identifies a critical window of increased susceptibility to As(III) that may have a lasting impact on female reproductive function. Copyright © 2013 Elsevier Inc. All rights reserved.

Accurate simulation of geometry, singlet-singlet and triplet-singlet excitation of cyclometalated iridium(III) complex.

PubMed

Wang, Jian; Bai, Fu-Quan; Xia, Bao-Hui; Zhang, Hong-Xing; Cui, Tian

2014-03-01

In the current contribution, we present a critical study of the theoretical protocol used for the determination of the electronic spectra properties of luminescent cyclometalated iridium(III) complex, [Ir(III)(ppy)₂H₂dcbpy]⁺ (where, ppy = 2-phenylpyridine, H₂dcbpy = 2,2'-bipyridine-4,4'-dicarboxylic acid), considered as a representative example of the various problems related to the prediction of electronic spectra of transition metal complex. The choice of the exchange-correlation functional is crucial for the validity of the conclusions that would be drawn from the numerical results. The influence of the exchange-correlation on geometry parameter and absorption/emission band, the role of solvent effects on time-dependent density function theory (TD-DFT) calculations, as well as the importance of the chosen proper procedure to optimize triplet excited geometry, have been thus examined in detail. From the obtained results, some general conclusions and guidelines are presented: i) PBE0 functional is the most accurate in prediction of ground state geometry; ii) the well-established B3LYP, B3P86, PBE0, and X3LYP have similar accuracy in calculation of absorption spectrum; and iii) the hybrid approach TD-DFT//CIS gives out excellent agreement in the evaluation of triplet excitation energy.

Glaucoma diagnostic capacity of optic nerve head haemoglobin measures compared with spectral domain OCT and HRT III confocal tomography.

PubMed

Mendez-Hernandez, Carmen; Rodriguez-Uña, Ignacio; Gonzalez-de-la Rosa, Manuel; Arribas-Pardo, Paula; Garcia-Feijoo, Julian

2016-11-01

The computer program laguna onhe determines optic nerve head haemoglobin (ONH Hb) on retinal photographs based on detecting colour differences. This study compares the diagnostic capacity of Laguna ONhE with that of spectral domain optical coherence tomography (OCT) and confocal tomography (HRT III). In a prospective, observational, cross-sectional study, glaucomatous (n = 66) and healthy (n = 52) eyes were examined by Spectralis OCT, HRT III and Laguna ONhE. The following Laguna ONhE variables were determined: ONH Hb across the vertical disc diameter (8&20 Hb), estimated cup-disc ratio (C/D) and the glaucoma discriminant function (GDF), which combines the slope of Hb amount with the mean in 8&20 Hb. The three diagnostic methods were compared by calculating areas under ROC curves (AUCs). Correlations between variables were assessed through Spearman's rho coefficient. Areas under ROC curves (AUCs) were 0.785 (95% CI: 0.700-0.863) for GDF, 0.807 (95% CI: 0.730-0.883) for OCT retinal nerve fibre layer thickness (OCT-RNFL) and 0.714 (95% CI: 0.618-0.810) and 0.721 (95% CI: 0.628-0.815) for the HRT III variable GPS (glaucoma probability score) and vertical C/D ratio, respectively. Glaucoma discriminant function (GDF) was correlated with OCT-RNFL (0.587, p 0.001; 0.507, p 0.045; and -0.119, p 0.713 for mild, moderate and advanced glaucoma, respectively), mostly so with inferior OCT-RNFL (0.622; p < 0.001). Glaucoma discriminant function (GDF)-HRT III correlations were lower (rim area 0.471, p < 0.0001; rim/disc area 0.426, p < 0.0001; vertical C/D -0.413, p < 0.0001; GPS -0.408, p < 0.0001; rim volume 0.341, p < 0.0001). Similar diagnostic power was observed for Laguna ONhE, Spectralis OCT and HRT III. © 2016 Acta Ophthalmologica Scandinavica Foundation. Published by John Wiley & Sons Ltd.

Measuring intellectual ability in children with cerebral palsy: can we do better?

PubMed

Sherwell, Sarah; Reid, Susan M; Reddihough, Dinah S; Wrennall, Jacquie; Ong, Ben; Stargatt, Robyn

2014-10-01

Standard intelligence tests such as the WPPSI-III have limitations when testing children with motor impairment. This study aimed to determine the proportion of children with cerebral palsy with sufficient verbal and motor skills to complete the WPPSI-III, to determine their comparative ability to complete tasks with and without a significant motor component, and to investigate short forms of the WPPSI-III as alternatives. Participants were 78 of 235 eligible 4-5 year old children with cerebral palsy resident in the Australian state of Victoria. Verbal IQ (VIQ), Performance IQ (PIQ), and Full-scale IQ (FSIQ) were determined using the WPPSI-III. Initial screening for pointing and verbal abilities determined which tests were attempted. The impact of speed was investigated by comparing scores on the Block Design subtest with and without an imposed time limit. FSIQ scores were calculated from two short forms of the WPPSI-III and compared to the full form. On screening, 16 children had inadequate pointing (14) and verbal abilities (2). FSIQ was obtained in 62 (82%) children. Strong associations were seen between completion of the entire test battery and topographical pattern, level of manual ability and level of gross motor function. Scores on subtests requiring manual ability were depressed relative to other scores. Children performed better using short forms of the WPPSI-III and, for a minority, when time limits were disregarded. In summary, children with cerebral palsy often lack the fine and gross motor skills necessary to complete the WPPSI-III, scoring relatively poorly on tasks requiring a fine motor response. Using short-form estimations of FSIQ comprised of subtests without a significant fine motor component has the potential to increase a child's FSIQ by approximately 5 points. These findings have important clinical implications when assessing a child with both motor and cognitive limitations. Copyright © 2014 Elsevier Ltd. All rights reserved.

N III Bowen Lines and Fluorescence Mechanism in the Symbiotic Star AG Peg

NASA Astrophysics Data System (ADS)

Hyung, Siek; Lee, Seong-Jae; Lee, Kang Hwan

2018-03-01

We have investigated the intensities and full width at half maximum (FWHM) of the high dispersion spectroscopic N III emission lines of AG Peg, observed with the Hamilton Echelle Spectrograph (HES) in three different epochs at Mt. Hamilton's Lick Observatory. The earlier theoretical Bowen line study assumed the continuum fluorescence effect, presenting a large discrepancy with the present data. Hence, we analyzed the observed N III lines assuming line fluorescence as the only suitable source: (1) The O III and N III resonance line profiles near λ 374 were decomposed, using the Gaussian function, and the contributions from various O III line components were determined. (2) Based on the theoretical resonant N III intensities, the expected N III Bowen intensities were obtained to fit the observed values. Our study shows that the incoming line photon number ratio must be considered to balance at each N III Bowen line level in the ultraviolet radiation according to the observed lines in the optical zone. We also found that the average FWHM of the N III Bowen lines was about 5 km·s-1 greater than that of the O III Bowen lines, perhaps due to the inherently different kinematic characteristics of their emission zones.

As(III) and As(V) sorption on iron-modified non-pyrolyzed and pyrolyzed biomass from Petroselinum crispum (parsley).

PubMed

Jiménez-Cedillo, M J; Olguín, M T; Fall, C; Colin-Cruz, A

2013-03-15

The sorption of As(III) and As(V) from aqueous solutions onto iron-modified Petroselinum crispum (PCFe) and iron-modified carbonaceous material from the pyrolysis of P. crispum (PCTTFe) was investigated. The modified sorbents were characterized with scanning electron microscopy. The sorbent elemental composition was determined with energy-dispersive X-ray spectroscopy (EDS). The principal functional groups from the sorbents were determined with FT-IR. The specific surfaces and points of zero charge (pzc) of the materials were also determined. As(III) and As(V) sorption onto the modified sorbents were performed in a batch system. After the sorption process, the As content in the liquid and solid phases was determined with atomic absorption and neutron activation analyses, respectively. After the arsenic sorption processes, the desorption of Fe from PCFe and PCTTFe was verified with atomic absorption spectrometry. The morphology of PC changed after iron modification. The specific area and pzc differed significantly between the iron-modified non-pyrolyzed and pyrolyzed P. crispum. The kinetics of the arsenite and arsenate sorption processes were described with a pseudo-second-order model. The Langmuir-Freundlich model provided the isotherms with the best fit. Less than 0.02% of the Fe was desorbed from the PCFe and PCTTFe after the As(III) and As(V) sorption processes. Copyright © 2013 Elsevier Ltd. All rights reserved.

Interactive effects of the ACE DD polymorphism with the NOS III homozygous G849T (Glu298-->Asp) variant in determining endothelial function in coronary artery disease.

PubMed

Schmidt, Michael A; Chakrabarti, Anjan K; Kehrer, Chris; Pfeninnger, Dana; Brook, Robert D; Kaciroti, Niko; Duvernoy, Claire; Killeen, Anthony A; Rajagopalan, Sanjay

2003-01-01

The products of nitric oxide synthase (NOS) and angiotensin-converting enzyme (ACE) play a critical role in determining vessel wall structure and function. Polymorphisms in both genes have been independently demonstrated to influence propensity to cardiovascular events. The purpose of this study was to determine the influence of the homozygous G849T (Glu298-->Asp) polymorphism in NOS III on peripheral conduit artery endothelial function and to elucidate the modifier role, if any, of a common ACE polymorphism. Three hundred and ninety-seven consecutive subjects presenting to the cardiac catheterization laboratory of the University of Michigan over a period of 18 months were recruited. DNA was extracted and polymerase chain reaction (PCR) analysis for ACE and NOS polymorphisms performed. Patients with homozygosity for G849T at both loci (TT) who belong to DD and II ACE genotype (groups 1 and 2) and those who are negative for this polymorphism (GG) and belong to either DD or II genotype (groups 3 and 4) were identified. The four groups then underwent determination of conduit endothelial function. Heterozygosity of Glu298-Asp or the ID variant of the ACE were not studied. Median FMD value in the TT-DD group was 0.20 (-3.17, 2.01) compared with 2.23% (-0.29, 4.17) in the GG-II group. Median values in the TT-II and the GG-DD groups were 3.04 (-1.16, 6.61) and 2.46% (-1.83, 6.52) respectively. These values were not statistically significant (p > 0.05 by one-way ANOVA). Median nitroglycerin-mediated dilation in the four groups did not differ between the four groups (p = NS by ANOVA). Atherosclerosis burdens as assessed by angiography were not different across the groups. In conclusion, the homozygous NOS III variant (GG) status does not seem to interact additively with the ACE homozygous DD genotype in determining flow-mediated vasodilation in individuals with established atherosclerosis and pre-existent endothelial dysfunction.

Direct regulation of RNA polymerase III transcription by RB, p53 and c-Myc.

PubMed

Felton-Edkins, Zoë A; Kenneth, Niall S; Brown, Timothy R P; Daly, Nicole L; Gomez-Roman, Natividad; Grandori, Carla; Eisenman, Robert N; White, Robert J

2003-01-01

The synthesis of tRNA and 5S rRNA by RNA polymerase (pol) III is cell cycle regulated in higher organisms. Overexpression of pol III products is a general feature of transformed cells. These observations may be explained by the fact that a pol III-specific transcription factor, TFIIIB, is strongly regulated by the tumor suppressors RB and p53, as well as the proto-oncogene product c-Myc. RB and p53 repress TFIIIB, but this restraint can be lost in tumors through a variety of mechanisms. In contrast, c-Myc binds and activates TFIIIB, causing potent induction of pol III transcription. Using chromatin immunoprecipitation and RNA interference, we show that c-Myc interacts with tRNA and 5S rRNA genes in transformed cervical cells, stimulating their expression. Availability of pol III products may be an important determinant of a cell's capacity to grow. The ability to regulate pol III output may therefore be integral to the growth control functions of RB, p53 and c-Myc.

Is junk DNA bunk? A critique of ENCODE.

PubMed

Doolittle, W Ford

2013-04-02

Do data from the Encyclopedia Of DNA Elements (ENCODE) project render the notion of junk DNA obsolete? Here, I review older arguments for junk grounded in the C-value paradox and propose a thought experiment to challenge ENCODE's ontology. Specifically, what would we expect for the number of functional elements (as ENCODE defines them) in genomes much larger than our own genome? If the number were to stay more or less constant, it would seem sensible to consider the rest of the DNA of larger genomes to be junk or, at least, assign it a different sort of role (structural rather than informational). If, however, the number of functional elements were to rise significantly with C-value then, (i) organisms with genomes larger than our genome are more complex phenotypically than we are, (ii) ENCODE's definition of functional element identifies many sites that would not be considered functional or phenotype-determining by standard uses in biology, or (iii) the same phenotypic functions are often determined in a more diffuse fashion in larger-genomed organisms. Good cases can be made for propositions ii and iii. A larger theoretical framework, embracing informational and structural roles for DNA, neutral as well as adaptive causes of complexity, and selection as a multilevel phenomenon, is needed.

Is junk DNA bunk? A critique of ENCODE

PubMed Central

Doolittle, W. Ford

2013-01-01

Do data from the Encyclopedia Of DNA Elements (ENCODE) project render the notion of junk DNA obsolete? Here, I review older arguments for junk grounded in the C-value paradox and propose a thought experiment to challenge ENCODE’s ontology. Specifically, what would we expect for the number of functional elements (as ENCODE defines them) in genomes much larger than our own genome? If the number were to stay more or less constant, it would seem sensible to consider the rest of the DNA of larger genomes to be junk or, at least, assign it a different sort of role (structural rather than informational). If, however, the number of functional elements were to rise significantly with C-value then, (i) organisms with genomes larger than our genome are more complex phenotypically than we are, (ii) ENCODE’s definition of functional element identifies many sites that would not be considered functional or phenotype-determining by standard uses in biology, or (iii) the same phenotypic functions are often determined in a more diffuse fashion in larger-genomed organisms. Good cases can be made for propositions ii and iii. A larger theoretical framework, embracing informational and structural roles for DNA, neutral as well as adaptive causes of complexity, and selection as a multilevel phenomenon, is needed. PMID:23479647

Poly(1-vinylimidazole) functionalized magnetic ion imprinted polymer for fast and selective extraction of trace gold in geological, environmental and biological samples followed by graphite furnace atomic absorption spectrometry detection

NASA Astrophysics Data System (ADS)

Zhao, Bingshan; He, Man; Chen, Beibei; Xu, Hongrun; Hu, Bin

2018-05-01

In this study, poly(1-vinylimidazole) functionalized gold ion imprinted polymer coated magnetic nanoparticles (MNPs@PVIM-Au-IIP) were prepared and characterized. The adsorption behaviors of the prepared MNPs@PVIM-Au-IIP toward gold ions (Au(III)) were studied, it was found that MNPs@PVIM-Au-IIP has good selectivity, high adsorption capacity (185.4 mg g-1) and fast adsorption kinetic for Au(III). Based on it, a new method of ion imprinted magnetic solid phase extraction (II-MSPE) coupled with graphite furnace atomic absorption spectrometry (GFAAS) detection was proposed for the analysis of trace Au(III) in real samples with complicated matrix. Factors affecting MSPE including sample pH, desorption reagent, elution concentration and volume, elution time, sample volume and adsorption time were optimized. With high enrichment factor of 100-fold, the detection limit of the proposed method is 7.9 ng L-1 for Au(III) with the relative standard deviation of 7.4% (c = 50 ng L-1, n = 7). In order to validate the accuracy of the proposed method, the Certified Reference Material of GBW07293 geological sample (platinpalladium ore) was analyzed, and the determined value was in good agreement with the certified value. The proposed II-MSPE-GFAAS method is simple, fast, selective, sensitive and has been successfully applied in the determination of trace Au in ore, sediment, environmental water and human urine samples with satisfactory results.

Intracellular versus extracellular accumulation of Hexavalent chromium reduction products by Geobacter sulfurreducens PCA.

PubMed

Gong, Yufeng; Werth, Charles J; He, Yaxue; Su, Yiming; Zhang, Yalei; Zhou, Xuefei

2018-05-10

Hexavalent chromium (Cr(VI)) reduction by Geobacter sulfurreducens PCA was evaluated in batch experiments, and the form and amounts of intracellular and extra-cellular Cr(VI) reduction products were determined over time. The first-order Cr(VI) reduction rate per unit mass of cells was consistent for different initial cell concentrations, and approximately equal to (2.065 ± 0.389) x 10 -9  mL CFU -1 h -1 . A portion of the reduced Cr(VI) products precipitated on Geobacter cell walls as Cr(III) and was bound via carboxylate functional groups, a portion accumulated inside Geobacter cells, and another portion existed as soluble Cr(III) or organo-Cr(III) released to solution. A mass balance analysis of total chromium in aqueous media, on cell walls, and inside cells was determined as a function of time, and with different initial cell concentrations. Mass balances were between 92% and 98%, and indicated Cr(VI) reduction products accumulate more on cell walls and inside cells with time and with increasing initial cell concentration, as opposed to particulates in aqueous solution. Reduced Cr(VI) products both in solution and on cell surfaces appear to form organo-Cr(III) complexes, and our results suggest that such complexes are more stable to reoxidation than aqueous Cr(III) or Cr(OH) 3 . Chromium inside cells is also likely more stable to reoxidation, both because it can form organic complexes, and it is separated by the cell membrane from solution conditions. Hence, Cr(VI) reduction products in groundwater during bioremediation may become more stable against re-oxidation, and may pose a lower risk to human health, over time and with greater initial biomass densities. Copyright © 2018 Elsevier Ltd. All rights reserved.

Multidisciplinary Treatment of Severe Osteogenesis Imperfecta: Functional Outcomes at Skeletal Maturity.

PubMed

Montpetit, Kathleen; Palomo, Telma; Glorieux, Francis H; Fassier, François; Rauch, Frank

2015-10-01

To determine the functional outcomes associated with long-term multidisciplinary treatment, intravenous bisphosphonate treatment, orthopedic surgery, and rehabilitation in children with severe osteogenesis imperfecta (OI) (diagnosed clinically as OI types III or IV). Retrospective study where outcomes were measured prospectively. Pediatric orthopedic hospital. Adolescents (N=41; age range, 15-21y) with severe OI (OI type III: n=17; OI type IV: n=24) who had started therapy before the age of 6 years, had received treatment for at least 10 years, and had achieved final height. Intravenous bisphosphonate treatment, orthopedic surgery, and rehabilitation. Pediatric Evaluation of Disability Inventory. At the time of the last available follow-up examination, none of the individuals diagnosed with OI type III (most severely affected group) was able to ambulate without ambulation aids, whereas 20 (83%) patients with OI type IV were able to ambulate without ambulation aids. Regarding self-care, we specifically assessed 8 skills that we deemed essential for living independently (grooming; dressing; toileting; bed, chair, toilet, tub, and car transfers). Only 6 (35%) of the youths with OI type III were able to complete all 8 items, whereas 23 (96%) individuals with OI type IV managed to perform all tasks. Teens with OI type III often needed assistance for the transfer to toilet, tub, and car and for personal hygiene and clothing management associated with toileting, usually because of limitations in upper-extremity function. These observations suggest that further improvements in the functional status of the most severely affected children with OI are contingent on advances in the clinical management of upper-extremity issues. Copyright © 2015 American Congress of Rehabilitation Medicine. Published by Elsevier Inc. All rights reserved.

32 CFR 989.3 - Responsibilities.

Code of Federal Regulations, 2014 CFR

2014-07-01

... environmental planning policy and provides oversight of the EIAP program. (ii) Determines the level of... § 989.1. (ii) Assists the environmental planning function and the Air Force Legal Services Agency, Trial Judiciary Division (AFLOA/JAJT), in planning and conducting public scoping meetings and hearings. (iii...

Probing chromium(III) from chromium(VI) in cells by a fluorescent sensor

NASA Astrophysics Data System (ADS)

Hu, Xiangquan; Chai, Jie; Liu, Yanfei; Liu, Bin; Yang, Binsheng

2016-01-01

Cellular uptake of Cr(VI), followed by its reduction to Cr(III) with the formation of kinetically inert Cr(III) complexes, is a complex process. To better understand its physiological and pathological functions, efficient methods for the monitoring of Cr(VI) are desired. In this paper a selective fluorescent probe L, rhodamine hydrazide bearing a benzo[b]furan-2-carboxaldehyde group, was demonstrated as a red chemosensor for Cr(III) at about 586 nm. This probe has been used to probe Cr(III) which is reduced from Cr(VI) by reductants such as glutathione (GSH), vitamin C, cysteine (Cys), H2O2 and Dithiothreitol (DTT) by fluorescence spectra. Cr(VI) metabolism in vivo is primarily driven by Vc and GSH. Vc could reduce CrO42 - to Cr(III) in a faster rate than GSH. The indirectly detection limit for Cr(VI) by L + GSH system was determined to be 0.06 μM at pH = 6.2. Moreover, the confocal microscopy image experiments indicated that Cr(VI) can be reduced to Cr(III) inside cells rapidly and the resulted Cr(III) can be captured and imaged timely by L.

In Vivo Determination of the Complex Elastic Moduli of Cetacean Head Tissue

DTIC Science & Technology

2013-09-30

of an ultrasonic Doppler vibration measurement system called NVMS developed at Georgia Tech iii. Algorithms have been developed to enable the...magnitude and phase of vibration to be determined as a function of range (tissue depth) along the ultrasonic beam. By measuring the differential phase of...The frequency dependence of the propagation speed is then used to determine the shear loss factor. The elastic properties of tissue phantoms

Role of Microbial Exopolymeric Substances (EPS) on Chromium Sorption and Transport in Heterogeneous Subsurface Soils: I. Cr(III) Complexation with EPS in Aqueous Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

C Kantar; H Demiray; N Dogan

2011-12-31

Chromium (III) binding by exopolymeric substances (EPS) isolated from Pseudomonas putida P18, Pseudomonas aeruginosa P16 and Pseudomonas stutzeri P40 strains were investigated by the determination of conditional stability constants and the concentration of functional groups using the ion-exchange experiments and potentiometric titrations. Spectroscopic (EXAFS) analysis was also used to obtain information on the nature of Cr(III) binding with EPS functional groups. The data from ion-exchange experiments and potentiometric titrations were evaluated using a non-electrostatic discrete ligand approach. The modeling results show that the acid/base properties of EPSs can be best characterized by invoking four different types of acid functional groupsmore » with arbitrarily assigned pK{sub a} values of 4, 6, 8 and 10. The analysis of ion-exchange data using the discrete ligand approach suggests that while the Cr binding by EPS from P. aeruginosa can be successfully described based on a reaction stoichiometry of 1:2 between Cr(III) and HL{sub 2} monoprotic ligands, the accurate description of Cr binding by EPSs extracted from P. putida and P. stutzeri requires postulation of 1:1 Cr(III)-ligand complexes with HL{sub 2} and HL{sub 3} monoprotic ligands, respectively. These results indicate that the carboxyl and/or phosphoric acid sites contribute to Cr(III) binding by microbial EPS, as also confirmed by EXAFS analysis performed in the current study. Overall, this study highlights the need for incorporation of Cr-EPS interactions into transport and speciation models to more accurately assess microbial Cr(VI) reduction and chromium transport in subsurface systems, including microbial reactive treatment barriers.« less

Role of microbial exopolymeric substances (EPS) on chromium sorption and transport in heterogeneous subsurface soils: I. Cr(III) complexation with EPS in aqueous solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kantar, C.; Dodge, C.; Demiray, H.

2011-01-26

Chromium (III) binding by exopolymeric substances (EPS) isolated from Pseudomonas putida P18, Pseudomonas aeruginosa P16 and Pseudomonas stutzeri P40 strains were investigated by the determination of conditional stability constants and the concentration of functional groups using the ion-exchange experiments and potentiometric titrations. Spectroscopic (EXAFS) analysis was also used to obtain information on the nature of Cr(III) binding with EPS functional groups. The data from ion-exchange experiments and potentiometric titrations were evaluated using a non-electrostatic discrete ligand approach. The modeling results show that the acid/base properties of EPSs can be best characterized by invoking four different types of acid functional groupsmore » with arbitrarily assigned pK{sub a} values of 4, 6, 8 and 10. The analysis of ion-exchange data using the discrete ligand approach suggests that while the Cr binding by EPS from P. aeruginosa can be successfully described based on a reaction stoichiometry of 1:2 between Cr(III) and HL{sub 2} monoprotic ligands, the accurate description of Cr binding by EPSs extracted from P. putida and P. stutzeri requires postulation of 1:1 Cr(III)-ligand complexes with HL{sub 2} and HL{sub 3} monoprotic ligands, respectively. These results indicate that the carboxyl and/or phosphoric acid sites contribute to Cr(III) binding by microbial EPS, as also confirmed by EXAFS analysis performed in the current study. Overall, this study highlights the need for incorporation of Cr-EPS interactions into transport and speciation models to more accurately assess microbial Cr(VI) reduction and chromium transport in subsurface systems, including microbial reactive treatment barriers.« less

Point defect reduction in MOCVD (Al)GaN by chemical potential control and a comprehensive model of C incorporation in GaN

NASA Astrophysics Data System (ADS)

Reddy, Pramod; Washiyama, Shun; Kaess, Felix; Kirste, Ronny; Mita, Seiji; Collazo, Ramon; Sitar, Zlatko

2017-12-01

A theoretical framework that provides a quantitative relationship between point defect formation energies and growth process parameters is presented. It enables systematic point defect reduction by chemical potential control in metalorganic chemical vapor deposition (MOCVD) of III-nitrides. Experimental corroboration is provided by a case study of C incorporation in GaN. The theoretical model is shown to be successful in providing quantitative predictions of CN defect incorporation in GaN as a function of growth parameters and provides valuable insights into boundary phases and other impurity chemical reactions. The metal supersaturation is found to be the primary factor in determining the chemical potential of III/N and consequently incorporation or formation of point defects which involves exchange of III or N atoms with the reservoir. The framework is general and may be extended to other defect systems in (Al)GaN. The utility of equilibrium formalism typically employed in density functional theory in predicting defect incorporation in non-equilibrium and high temperature MOCVD growth is confirmed. Furthermore, the proposed theoretical framework may be used to determine optimal growth conditions to achieve minimum compensation within any given constraints such as growth rate, crystal quality, and other practical system limitations.

Preparation of microspheric Fe(III)-ion imprinted polymer for selective solid phase extraction

NASA Astrophysics Data System (ADS)

Ara, Behisht; Muhammad, Mian; Salman, Muhammad; Ahmad, Raees; Islam, Noor; Zia, Tanveer ul Haq

2018-03-01

In this research work, an Fe(III)-IIP was prepared using methacrylic acid as monomer, divinylbenzene as cross-linker, azobisisobutyronitrile as initiator. The ion imprinted polymer was functionalized with Fe(III)8-hydroxy quinolone complex under thermal conditions by copolymerization with the monomer and the cross-linker. The prepared Fe(III)-ion imprinted polymer (IIP) and non-ion imprinted polymer (Non-IIP) were characterized with fourier transform-infrared spectroscopy, scanning electron microscopic analysis and thermal gravimetric analysis. The polymer showed a good stability to thermal analysis up to a temperature of 500 °C. The size of the polymer obtained was 1 µm, large enough to be filtered easily. At pH 2.5 more affinity was observed with ion imprinted polymer in comparison to non-ion imprinted polymer. For the kinetic study, the most linear and rhythmical relation were seen in pseudo second order. The maximum sorption capacity of Fe(III) ions on Fe(III)-IIP and non-IIP was 170 and 30.0 µmolg-1, respectively. The relative selectivity factor (αr) values of Fe(III)/Fe(II), Fe(III)/Al(III) and Fe(III)/Cr(III) were 151.0, 84.6 and 91.9, respectively. The preconcentration factor was found to be 240. The developed method was successfully applied to the determination of trace Fe in the drinking water.

Aluminum(III) interferes with the structure and the activity of the peptidyl-prolyl cis-trans isomerase (Pin1): a new mechanism contributing to the pathogenesis of Alzheimer's disease and cancers?

PubMed

Wang, Jing-Zhang; Liu, Ji; Lin, Tao; Han, Yong-Guang; Luo, Yue; Xi, Lei; Du, Lin-Fang

2013-09-01

The enzyme peptidyl-prolyl cis-trans isomerase (Pin1) may play an important role in preventing the development of Alzheimer's disease (AD). The structural and functional stability of Pin1 is extremely important. Previously, we have determined the stability of Pin1 under stressed conditions, such as thermal treatment and acidic-pH. Considering that aluminum (Al(III)) is well known for its potential neurotoxicity in the pathogenesis of AD, we examined whether Al(III) affects the structure and function of Pin1, by means of a PPIase activity assay, intrinsic fluorescence, circular dichroism (CD) spectroscopy, FTIR, and differential scanning calorimetry (DSC). The intrinsic tryptophan fluorescence measurements mainly show that Al(III) may bind to the clusters nearby W11 and W34 in the WW domain of Pin1, quenching the intrinsic fluorescence of the two tryptophan residues, which possibly results in the decreased binding affinity of Pin1 to substrates. The secondary structural analysis as revealed by FTIR and CD measurements indicate that Al(III) induces the increase in β-sheet and the decrease in α-helix in Pin1. Furthermore, the changes of the thermodynamic parameters for Pin1 as monitored by DSC confirm that the thermal stability of Pin1 significantly increases in the presence of Al(III). The Al(III)-induced structural changes of Pin1 result in a sharp decrease of the PPIase activity of Pin1. To some extent, our research is suggestive that Al(III) may inhibit the isomerization activity of Pin1 in vivo, which may contribute to the pathogenesis of AD. Copyright © 2013. Published by Elsevier Inc.

Chromium(III)-imprinted silica gel for speciation analysis of chromium in environmental water samples with ICP-MS detection.

PubMed

Zhang, Nan; Suleiman, Jibrin Sabo; He, Man; Hu, Bin

2008-04-15

A new chromium(III)-imprinted 3-(2-aminoethylamino) propyltrimethoxysilane (AAPTS)-functionalized silica gel sorbent was synthesized by a surface imprinting technique and was employed as a selective solid-phase extraction material for speciation analysis of chromium in environmental water samples prior to its determination by inductively coupled plasma mass spectrometry (ICP-MS). The prepared Cr(III)-imprinted silica gel shows the selectivity coefficient of more than 700 for Cr(III) in the presence of Mn(II). The static adsorption capacity of the ion-imprinted and non-imprinted sorbent for Cr(III) were 30.5 mg g(-1) and 13.4 mg g(-1). It was also found that Cr(VI) could be adsorbed at low pH by the prepared imprinted silica gel, and this finding makes it feasible to enrich and determine Cr(VI) at low pH without adding reducing reagents. The imprinted silica gel sorbent offered a fast kinetics for the adsorption and desorption of both chromium species. Under the optimized conditions, the detection limits of 4.43 pg mL(-1) and 8.30 pg mL(-1) with the relative standard deviations (R.S.D.s) of 4.44% and 4.41% (C=0.5 ng mL(-1), n=7) for Cr(III) and Cr(VI) were obtained, respectively. The proposed method was successfully applied to the speciation of trace chromium in environmental water samples. To validate the proposed method, two certified reference materials were analyzed and the determined values were in a good agreement with the certified values. The developed method is rapid, selective, sensitive and applicable for the speciation of trace chromium in environmental water samples.

Extraction of water and speciation of trivalent lanthanides and americium in organophosphorus extractants

DOE PAGES

Gullekson, Brian J.; Breshears, Andrew T.; Brown, M. Alex; ...

2016-11-29

Complexes of the trivalent lanthanides and Am with di-2-ethylhexylphosphoric acid (HDEHP) dissolved in an aliphatic diluent were probed with UV–vis, X-ray absorption fine structure, and time-resolved fluorescence spectroscopy while the water concentration was determined by Karl Fischer titrations. In particular, our work focuses on the Nd-hypersensitive UV–vis absorbance region to identify the cause of changing absorbance values at 570 and 583 nm in relation to the pseudooctahedral Nd environment when coordinated with three HDEHP dimers. In contrast to recently reported interpretations, we establish that while impurities have an effect on this electronic transition band, a high water content can causemore » distortion of the pseudooctahedral symmetry of the six-coordinate Nd, resembling the reported spectra of the seven-coordinate Nd compounds. Extended X-ray absorption fine structure analysis of the Nd in high-concentration HDEHP solutions also points to an increase in the coordination number from 6 to 7. The spectral behavior of other lanthanides (Pr, Ho, Sm, and Er) and Am III as a function of the HDEHP concentration suggests that water coordination with the metal likely depends on the metal’s effective charge. Fluorescence data using lifetime studies and excitation and emission spectra support the inclusion of water in the Eu coordination sphere. Further, the role of the effective charge was confirmed by a comparison of the Gibbs free energies of six- and seven-coordinate La-HDEHP–H 2O and Lu-HDEHP–H 2O complexes using density functional theory. In contrast, HEH[EHP], the phosphonic acid analogue of HDEHP, exhibits a smaller capacity for water, and the electronic absorption spectra of Nd or Am appear to be unchanged, although the Pr spectra show a noticeable change in intensity as a function of the water content. As a result, electronic absorption extinction coefficients of Am III, Nd III, Pr III, Sm III, Er III, and Ho III as a function of the HDEHP concentration are reported for the first time.« less

Extraction of water and speciation of trivalent lanthanides and americium in organophosphorus extractants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gullekson, Brian J.; Breshears, Andrew T.; Brown, M. Alex

Complexes of the trivalent lanthanides and Am with di-2-ethylhexylphosphoric acid (HDEHP) dissolved in an aliphatic diluent were probed with UV–vis, X-ray absorption fine structure, and time-resolved fluorescence spectroscopy while the water concentration was determined by Karl Fischer titrations. In particular, our work focuses on the Nd-hypersensitive UV–vis absorbance region to identify the cause of changing absorbance values at 570 and 583 nm in relation to the pseudooctahedral Nd environment when coordinated with three HDEHP dimers. In contrast to recently reported interpretations, we establish that while impurities have an effect on this electronic transition band, a high water content can causemore » distortion of the pseudooctahedral symmetry of the six-coordinate Nd, resembling the reported spectra of the seven-coordinate Nd compounds. Extended X-ray absorption fine structure analysis of the Nd in high-concentration HDEHP solutions also points to an increase in the coordination number from 6 to 7. The spectral behavior of other lanthanides (Pr, Ho, Sm, and Er) and Am III as a function of the HDEHP concentration suggests that water coordination with the metal likely depends on the metal’s effective charge. Fluorescence data using lifetime studies and excitation and emission spectra support the inclusion of water in the Eu coordination sphere. Further, the role of the effective charge was confirmed by a comparison of the Gibbs free energies of six- and seven-coordinate La-HDEHP–H 2O and Lu-HDEHP–H 2O complexes using density functional theory. In contrast, HEH[EHP], the phosphonic acid analogue of HDEHP, exhibits a smaller capacity for water, and the electronic absorption spectra of Nd or Am appear to be unchanged, although the Pr spectra show a noticeable change in intensity as a function of the water content. As a result, electronic absorption extinction coefficients of Am III, Nd III, Pr III, Sm III, Er III, and Ho III as a function of the HDEHP concentration are reported for the first time.« less

Examination of DSM-5 Section III avoidant personality disorder in a community sample.

PubMed

Sellbom, Martin; Carmichael, Kieran L C; Liggett, Jacqueline

2017-11-01

The current research evaluated the continuity between DSM-5 Section II and Section III diagnostic operationalizations of avoidant personality disorder (AvPD). More specifically, the study had three aims: (1) to examine which personality constructs comprise the optimal trait constellation for AvPD; (2) to investigate the utility of the proposed structure of the Section III AvPD diagnosis, in regard to combining functional impairment (criterion A) and a dimensional measure of personality (criterion B) variables; and (3) to determine whether AvPD-specific impairment confers incremental meaningful contribution above and beyond general impairment in personality functioning. A mixed sample of 402 university and community participants was recruited, and they were administered multiple measures of Section II PD, personality traits, and personality impairment. A latent measurement model approach was used to analyse data. Results supported the general continuity between Section II and Section III of the DSM-5; however, three of the four main criterion B traits were the stronger predictors. There was also some support for the trait unassertiveness augmenting the criterion B trait profile. The combination of using functional impairment criteria (criterion A) and dimensional personality constructs (criterion B) in operationalizing AvPD was supported; however, the reliance of disorder-specific over general impairment for criterion A was not supported. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

[Evaluation of memory in acquired brain injury: a comparison between the Wechsler Memory Scale and the Rivermead Behaviour Memory Test].

PubMed

Guinea-Hidalgo, A; Luna-Lario, P; Tirapu-Ustárroz, J

Learning processes and memory are frequently compromised in acquired brain injury (ABI), while at the same time such involvement is often heterogeneous and a source of deficits in other cognitive capacities and significant functional limitations. A good neuropsychological evaluation of memory is designed to study not only the type, intensity and nature of the problems, but also the way they manifest in daily life. This study examines the correlation between a traditional memory test, the Wechsler Memory Scale-III (WMS-III), and a memory test that is considered to be functional, the Rivermead Behavioural Memory Test (RBMT), in a sample of 60 patients with ABI. All the correlations that were observed were moderate. Greater correlations were found among the verbal memory subtests than among the visual memory tests. An important number of subjects with below-normal scalar scores on the WMS-III correctly performed (either fully or partially) the corresponding test in the RBMT. The joint use of the WMS-III and RBMT in evaluation can provide a more comprehensive analysis of the memory deficits and their rehabilitation. The lower scores obtained in the WMS-III compared to those of the RBMT indicate greater sensitivity of the former. Nevertheless, further testing needs to be carried out in the future to compare the performance in the tests after the patients and those around them have subjectively assessed their functional limitations. This would make it possible to determine which of the two tests offers the best balance between sensitivity and specificity, as well as a higher predictive value.

Psychometric properties and validation of the Italian version of the Family Assessment Measure Third Edition - Short Version - in a nonclinical sample.

PubMed

Pellerone, Monica; Ramaci, Tiziana; Parrello, Santa; Guariglia, Paola; Giaimo, Flavio

2017-01-01

Family functioning plays an important role in developing and maintaining dysfunctional behaviors, especially during adolescence. The lack of indicators of family functioning, as determinants of personal and interpersonal problems, represents an obstacle to the activities aimed at developing preventive and intervention strategies. The Process Model of Family Functioning provides a conceptual framework organizing and integrating various concepts into a comprehensive family assessment; this model underlines that through the process of task accomplishment, each family meets objectives central to its life as a group. The Family Assessment Measure Third Edition (FAM III), based on the Process Model of Family Functioning, is among the most frequently used self-report instruments to measure family functioning. The present study aimed to evaluate the psychometric properties of the Italian version of the Family Assessment Measure Third Edition - Short Version (Brief FAM-III). It consists of three modules: General Scale, which evaluates the family as a system; Dyadic Relationships Scale, which examines how each family member perceives his/her relationship with another member; and Self-Rating Scale, which indicates how each family member is perceived within the nucleus. The developed Brief FAM-III together with the Family Assessment Device were administered to 484 subjects, members of 162 Italian families, formed of 162 fathers aged between 35 and 73 years; 162 mothers aged between 34 and 69 years; and 160 children aged between 12 and 35 years. Correlation, paired-sample t -test, and reliability analyses were carried out. General item analysis shows good indices of reliability with Cronbach's α coefficients equal to 0.96. The Brief FAM-III has satisfactory internal consistency, with Cronbach's α equal to 0.90 for General Scale, 0.94 for Dyadic Relationships Scale, and 0.88 for the Self-Rating Scale. The Brief FAM-III can be a psychometrically reliable and valid measure for the assessment of family strengths and weaknesses within Italian contexts. The instrument can be used to obtain an overall idea of family functioning, for the purposes of preliminary screening, and for monitoring family functioning over time or during treatment.

Psychometric properties and validation of the Italian version of the Family Assessment Measure Third Edition – Short Version – in a nonclinical sample

PubMed Central

Pellerone, Monica; Ramaci, Tiziana; Parrello, Santa; Guariglia, Paola; Giaimo, Flavio

2017-01-01

Background Family functioning plays an important role in developing and maintaining dysfunctional behaviors, especially during adolescence. The lack of indicators of family functioning, as determinants of personal and interpersonal problems, represents an obstacle to the activities aimed at developing preventive and intervention strategies. The Process Model of Family Functioning provides a conceptual framework organizing and integrating various concepts into a comprehensive family assessment; this model underlines that through the process of task accomplishment, each family meets objectives central to its life as a group. The Family Assessment Measure Third Edition (FAM III), based on the Process Model of Family Functioning, is among the most frequently used self-report instruments to measure family functioning. Materials and methods The present study aimed to evaluate the psychometric properties of the Italian version of the Family Assessment Measure Third Edition – Short Version (Brief FAM-III). It consists of three modules: General Scale, which evaluates the family as a system; Dyadic Relationships Scale, which examines how each family member perceives his/her relationship with another member; and Self-Rating Scale, which indicates how each family member is perceived within the nucleus. The developed Brief FAM-III together with the Family Assessment Device were administered to 484 subjects, members of 162 Italian families, formed of 162 fathers aged between 35 and 73 years; 162 mothers aged between 34 and 69 years; and 160 children aged between 12 and 35 years. Correlation, paired-sample t-test, and reliability analyses were carried out. Results General item analysis shows good indices of reliability with Cronbach’s α coefficients equal to 0.96. The Brief FAM-III has satisfactory internal consistency, with Cronbach’s α equal to 0.90 for General Scale, 0.94 for Dyadic Relationships Scale, and 0.88 for the Self-Rating Scale. Conclusion The Brief FAM-III can be a psychometrically reliable and valid measure for the assessment of family strengths and weaknesses within Italian contexts. The instrument can be used to obtain an overall idea of family functioning, for the purposes of preliminary screening, and for monitoring family functioning over time or during treatment. PMID:28280402

A novel sensor for monitoring of iron(III) ions based on porphyrins.

PubMed

Vlascici, Dana; Fagadar-Cosma, Eugenia; Popa, Iuliana; Chiriac, Vlad; Gil-Agusti, Mayte

2012-01-01

Three A(3)B porphyrins with mixed carboxy-, phenoxy-, pyridyl-, and dimethoxy-substituent functionalization on the meso-phenyl groups were obtained by multicomponent synthesis, fully characterized and used as ionophores for preparing PVC-based membrane sensors selective to iron(III). The membranes have an ionophore:PVC:plasticizer composition ratio of 1:33:66. Sodium tetraphenylborate was used as additive (20 mol% relative to ionophore). The performance characteristics (linear concentration range, slope and selectivity) of the sensors were investigated. The best results were obtained for the membrane based on 5-(4-carboxyphenyl)-10,15,20-tris(4-phenoxyphenyl)-porphyrin plasticized with bis(2-ethylhexyl)sebacate, in a linear range from 1 × 10(-7)-1 × 10(-1) M with a slope of 21.6 mV/decade. The electrode showed high selectivity with respect to alkaline and heavy metal ions and a response time of 20 s. The influence of pH on the sensor response was studied. The sensor was used for a period of six weeks and the utility has been tested for the quantitative determination of Fe(III) in recovered solutions from spent lithium ion batteries and for the quantitative determination of Fe(III) in tap water samples.

Modification and benchmarking of SKYSHINE-III for use with ISFSI cask arrays

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hertel, N.E.; Napolitano, D.G.

1997-12-01

Dry cask storage arrays are becoming more and more common at nuclear power plants in the United States. Title 10 of the Code of Federal Regulations, Part 72, limits doses at the controlled area boundary of these independent spent-fuel storage installations (ISFSI) to 0.25 mSv (25 mrem)/yr. The minimum controlled area boundaries of such a facility are determined by cask array dose calculations, which include direct radiation and radiation scattered by the atmosphere, also known as skyshine. NAC International (NAC) uses SKYSHINE-III to calculate the gamma-ray and neutron dose rates as a function of distance from ISFSI arrays. In thismore » paper, we present modifications to the SKYSHINE-III that more explicitly model cask arrays. In addition, we have benchmarked the radiation transport methods used in SKYSHINE-III against {sup 60}Co gamma-ray experiments and MCNP neutron calculations.« less

Structural, luminescence, thermodynamic and theoretical studies on mononuclear complexes of Eu(III) with pyridine monocarboxylate-N-oxides in aqueous solution

NASA Astrophysics Data System (ADS)

Dumpala, Rama Mohana Rao; Rawat, Neetika; Boda, Anil; Ali, Sk. Musharaf; Tomar, B. S.

2018-02-01

The mononuclear complexes formed by Eu(III) with three isomeric pyridine monocarboxylate-N-oxides namely picolinic acid-N-oxide (PANO), nicotinic acid-N-oxide (NANO) and isonicotinic acid-N-oxide (IANO) in aqueous solutions were studied by potentiometry, luminescence spectroscopy and isothermal titration calorimetry (ITC) to determine the speciation, coordination, luminescence properties and thermodynamic parameters of the complexes formed during the course of the reaction. More stable six membered chelate complexes with stoichiometry (MLi, i = 1-4) are formed by Eu(III) with PANO while non chelating ML and ML2 complexes are formed by NANO and IANO. The stability of Eu(III) complexes follow the order PANO > IANO > NANO. The ITC studies inferred an endothermic and innersphere complex formation of Eu(III)-PANO and Eu(III)-IANO whereas an exothermic and outer-sphere complex formation for Eu(III)-NANO. The luminescence life time data further supported the ITC results. Density functional theoretical calculations were carried out to optimize geometries of the complexes and to estimate the energies, structural parameters (bond distances, bond angles) and charges on individual atoms of the same. Theoretical approximations are found to be in good agreement with the experimental observations.

Evaluation of XD/A Plus and ST8G films for cephalometric radiography with Grenex G8 and BH-III screens.

PubMed

Wakoh, M; Farman, A G; Scarfe, W C; Shibuya, H; Nishikawa, K; Kuroyanagi, K

1997-02-01

Sensitometric properties, clinical image quality, and patient dose requirements are important considerations when selecting film for cephalometrics. Two recently released films, XD/A Plus and ST 8G green sensitive films, were studied. The films were each combined with Grenex G8 (Fuji Medical) green-fluorescing matched and BH-III (Kasei Optonix) blue-fluorescing mismatched intensifying screens. The density response and resolution for each screen-film combination were evaluated by use of the characteristic curve and modulation transfer function. The kilovoltage settings providing clinically acceptable images were assessed individually by 12 observers. Clinically acceptable images for each combination were also compared, and the skin entrance doses in the temporomandibular joint region were determined. The average contrast at the most effective density range was found to be slightly higher for the BH-III group than for the G8 group. The modulation transfer function for the BH-III group was inferior to that for the G8 screens. There were no significant differences in diagnostically acceptable image quality among the four combinations; nevertheless the BH-III screen group required two to three times more exposure than the G8 screen group. XD/A Plus and ST8G films provide acceptable image detail for cephalometrics. To minimize the patient dose they should be used with green-emitting screens.

Optimal dose selection accounting for patient subpopulations in a randomized Phase II trial to maximize the success probability of a subsequent Phase III trial.

PubMed

Takahashi, Fumihiro; Morita, Satoshi

2018-02-08

Phase II clinical trials are conducted to determine the optimal dose of the study drug for use in Phase III clinical trials while also balancing efficacy and safety. In conducting these trials, it may be important to consider subpopulations of patients grouped by background factors such as drug metabolism and kidney and liver function. Determining the optimal dose, as well as maximizing the effectiveness of the study drug by analyzing patient subpopulations, requires a complex decision-making process. In extreme cases, drug development has to be terminated due to inadequate efficacy or severe toxicity. Such a decision may be based on a particular subpopulation. We propose a Bayesian utility approach (BUART) to randomized Phase II clinical trials which uses a first-order bivariate normal dynamic linear model for efficacy and safety in order to determine the optimal dose and study population in a subsequent Phase III clinical trial. We carried out a simulation study under a wide range of clinical scenarios to evaluate the performance of the proposed method in comparison with a conventional method separately analyzing efficacy and safety in each patient population. The proposed method showed more favorable operating characteristics in determining the optimal population and dose.

Classification of pediatric functional gastrointestinal disorders related to abdominal pain using Rome III vs. Rome IV criterions.

PubMed

Edwards, Trent; Friesen, Craig; Schurman, Jennifer V

2018-03-17

The primary purpose of this study was to compare Rome III and IV evaluation criteria for irritable bowel syndrome (IBS), functional dyspepsia (FD), and an overlap syndrome consisting of both IBS and FD by assessing the frequency of each diagnosis in a population of children with chronic abdominal pain. Frequencies of Rome IV FD subtypes of postprandial distress syndrome (PDS) and epigastric pain syndrome (EPS) were determined and FD/IBS overlap symptom associations were also assessed. We conducted a cross-sectional retrospective chart review of 106 pediatric patients who had completed standardized medical histories as part of their evaluation for chronic abdominal pain. The patients ranged from eight to 17 years of age and reported having abdominal pain at least weekly for 8 weeks. Patients whose evaluation revealed gastrointestinal disease were excluded. The patients' diagnoses were determined by a single pediatric gastroenterologist utilizing the specific criteria for Rome III and IV, respectively. Patients were significantly more likely to be diagnosed with FD (84.9% vs. 52.8%), IBS (69.8% vs. 34%), and FD/IBS overlap (58.5% vs. 17.9%) by Rome IV criteria, as compared to Rome III criteria. With regard to Rome IV FD subtypes, 81.1% fulfilled criteria for PDS, 11.1% fulfilled criteria for EPS, 6.7% fulfilled criteria for both, and 1.1% did not fulfill criteria for either. Finally, we found an increased frequency of diarrhea and pain with eating in the overlap group compared to the non-overlap group of Rome III, while only an increased frequency of diarrhea was found in the overlap group compared to the non-overlap group of Rome IV. Our data demonstrate that utilizing Rome IV criteria, as compared to Rome III, results in an increase in the diagnosis of FD, a two-fold increase in the diagnosis of IBS, and a three-fold increase in the diagnosis of FD/IBS overlap. Rome IV criteria appears to result in greater heterogeneity within diagnostic categories. It is important to determine whether Rome IV diagnoses are predictive of treatment response, and if so, whether assessing symptom variability within a diagnosis will enhance the ability to select patients for a particular treatment.

Relations between the Woodcock-Johnson III Clinical Clusters and Measures of Executive Functions from the Delis-Kaplan Executive Function System

ERIC Educational Resources Information Center

Floyd, Randy G.; McCormack, Allison C.; Ingram, Elizabeth L.; Davis, Amy E.; Bergeron, Renee; Hamilton, Gloria

2006-01-01

This study examined the convergent relations between scores from four clinical clusters from the Woodcock-Johnson III Tests of Cognitive Abilities (WJ III) and measures of executive functions using a sample of school-aged children and a sample of adults. The WJ III clinical clusters included the Working Memory, Cognitive Fluency, Broad Attention,…

Proteomics and genetic analyses reveal the effects of arsenite oxidation on metabolic pathways and the roles of AioR in Agrobacterium tumefaciens GW4.

PubMed

Shi, Kaixiang; Wang, Qian; Fan, Xia; Wang, Gejiao

2018-04-01

A heterotrophic arsenite [As(III)]-oxidizing bacterium Agrobacterium tumefaciens GW4 isolated from As(III)-rich groundwater sediment showed high As(III) resistance and could oxidize As(III) to As(V). The As(III) oxidation could generate energy and enhance growth, and AioR was the regulator for As(III) oxidase. To determine the related metabolic pathways mediated by As(III) oxidation and whether AioR regulated other cellular responses to As(III), isobaric tags for relative and absolute quantitation (iTRAQ) was performed in four treatments, GW4 (+AsIII)/GW4 (-AsIII), GW4-ΔaioR (+AsIII)/GW4-ΔaioR (-AsIII), GW4-ΔaioR (-AsIII)/GW4 (-AsIII) and GW4-ΔaioR (+AsIII)/GW4 (+AsIII). A total of 41, 71, 82 and 168 differentially expressed proteins were identified, respectively. Using electrophoretic mobility shift assay (EMSA) and qRT-PCR, 12 genes/operons were found to interact with AioR. These results indicate that As(III) oxidation alters several cellular processes related to arsenite, such as As resistance (ars operon), phosphate (Pi) metabolism (pst/pho system), TCA cycle, cell wall/membrane, amino acid metabolism and motility/chemotaxis. In the wild type with As(III), TCA cycle flow is perturbed, and As(III) oxidation and fermentation are the main energy resources. However, when strain GW4-ΔaioR lost the ability of As(III) oxidation, the TCA cycle is the main way to generate energy. A regulatory cellular network controlled by AioR is constructed and shows that AioR is the main regulator for As(III) oxidation, besides, several other functions related to As(III) are regulated by AioR in parallel. Copyright © 2018 Elsevier Ltd. All rights reserved.

Mechanistic Study of the Oxidative Coupling of Styrene with 2-Phenylpyridine Derivatives Catalyzed by Cationic Rhodium( III) via C–H Activation

PubMed Central

Brasse, Mikaël; Cámpora, Juan; Ellman, Jonathan A.; Bergman, Robert G.

2013-01-01

The Rh(III) catalyzed oxidative coupling of alkenes with arenes provides a greener alternative to the classical Heck reaction for the synthesis of arene-functionalized alkenes. The present mechanistic study gives insights for the rational development of this key transformation. The catalyst resting states and the rate law of the reaction have been identified. The reaction rate is solely dependent on catalyst and alkene concentrations and the rate determining step is the migratory insertion of alkene into a Rh–C(aryl) bond. PMID:23590843

Reactivity of a Cobalt(III)–Hydroperoxo Complex in Electrophilic Reactions

DOE PAGES

Shin, Bongki; Sutherlin, Kyle D.; Ohta, Takehiro; ...

2016-11-15

The reactivity of mononuclear metal-hydroperoxo adducts has fascinated researchers in many areas due to their diverse biological and catalytic processes. In this study, a mononuclear cobalt(III)-peroxo complex bearing a tetradentate macrocyclic ligand, [Co III(Me 3-TPADP)(O 2)] + (Me 3-TPADP = 3,6,9-trimethyl-3,6,9-triaza-1(2,6)-pyridinacyclodecaphane), was prepared by reacting [Co II(Me 3-TPADP)(CH 3CN) 2] 2+ with H 2O 2 in the presence of triethylamine. Upon protonation, the cobalt(III)- peroxo intermediate was converted into a cobalt(III)-hydroperoxo complex, [Co III(Me 3-TPADP)(O 2H)(CH 3CN)] 2+. The mononuclear cobalt(III)-peroxo and -hydroperoxo intermediates were characterized by a variety of physicochemical methods. Results of electrospray ionization mass spectrometry clearly showmore » the transformation of the intermediates: the peak at m/z 339.2 assignable to the cobalt(III)-peroxo species disappears with concomitant growth of the peak at m/z 190.7 corresponding to the cobalt(III)-hydroperoxo complex (with bound CH 3CN). Isotope labeling experiments further support the existence of the cobalt(III)-peroxo and -hydroperoxo complexes. In particular, the O-O bond stretching frequency of the cobalt(III)-hydroperoxo complex was determined to be 851 cm -1 for 16O 2H samples (803 cm -1 for 18O 2H samples) and its Co-O vibrational energy was observed at 571 cm -1 for 16O 2H samples (551 cm -1 for 18O 2H samples; 568 cm -1 for 16O 2 2H samples) by resonance Raman spectroscopy. Reactivity studies performed with the cobalt(III)-peroxo and -hydroperoxo complexes in organic functionalizations reveal that the latter is capable of conducting oxygen atom transfer with an electrophilic character, whereas the former exhibits no oxygen atom transfer reactivity under the same reaction conditions. Alternatively, the cobalt(III)-hydroperoxo complex does not perform hydrogen atom transfer reactions, while analogous low-spin Fe(III)-hydroperoxo complexes are capable of this reactivity. Density function theory calculations indicate that this lack of reactivity is due to the high free energy cost of O-O bond homolysis that would be required to produce the hypothetical Co(IV)-oxo product.« less

Reactivity of a Cobalt(III)–Hydroperoxo Complex in Electrophilic Reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shin, Bongki; Sutherlin, Kyle D.; Ohta, Takehiro

The reactivity of mononuclear metal-hydroperoxo adducts has fascinated researchers in many areas due to their diverse biological and catalytic processes. In this study, a mononuclear cobalt(III)-peroxo complex bearing a tetradentate macrocyclic ligand, [Co III(Me 3-TPADP)(O 2)] + (Me 3-TPADP = 3,6,9-trimethyl-3,6,9-triaza-1(2,6)-pyridinacyclodecaphane), was prepared by reacting [Co II(Me 3-TPADP)(CH 3CN) 2] 2+ with H 2O 2 in the presence of triethylamine. Upon protonation, the cobalt(III)- peroxo intermediate was converted into a cobalt(III)-hydroperoxo complex, [Co III(Me 3-TPADP)(O 2H)(CH 3CN)] 2+. The mononuclear cobalt(III)-peroxo and -hydroperoxo intermediates were characterized by a variety of physicochemical methods. Results of electrospray ionization mass spectrometry clearly showmore » the transformation of the intermediates: the peak at m/z 339.2 assignable to the cobalt(III)-peroxo species disappears with concomitant growth of the peak at m/z 190.7 corresponding to the cobalt(III)-hydroperoxo complex (with bound CH 3CN). Isotope labeling experiments further support the existence of the cobalt(III)-peroxo and -hydroperoxo complexes. In particular, the O-O bond stretching frequency of the cobalt(III)-hydroperoxo complex was determined to be 851 cm -1 for 16O 2H samples (803 cm -1 for 18O 2H samples) and its Co-O vibrational energy was observed at 571 cm -1 for 16O 2H samples (551 cm -1 for 18O 2H samples; 568 cm -1 for 16O 2 2H samples) by resonance Raman spectroscopy. Reactivity studies performed with the cobalt(III)-peroxo and -hydroperoxo complexes in organic functionalizations reveal that the latter is capable of conducting oxygen atom transfer with an electrophilic character, whereas the former exhibits no oxygen atom transfer reactivity under the same reaction conditions. Alternatively, the cobalt(III)-hydroperoxo complex does not perform hydrogen atom transfer reactions, while analogous low-spin Fe(III)-hydroperoxo complexes are capable of this reactivity. Density function theory calculations indicate that this lack of reactivity is due to the high free energy cost of O-O bond homolysis that would be required to produce the hypothetical Co(IV)-oxo product.« less

Reliability of psychiatric diagnosis in hospitalized adolescents. Interrater agreement using DSM-III.

PubMed

Strober, M; Green, J; Carlson, G

1981-02-01

To determine the reliability of psychiatric diagnosis in hospitalized adolescents, 95 consecutively admitted patients were diagnosed independently by two experienced clinicians using DSM-III criteria. Diagnostic judgments were based on joint interview of the patient via a structured mental-status examination, nursing observations, and referral materials. Concordance was analyzed by the kappa coefficient. A total of 13 DSM-III categories were used to classify this cohort, with the majority of categories representing traditional syndromes of functional psychopathology. There was complete agreement between the raters for more than three fourths of the patients. Levels of agreement for the categories of schizophrenia and major affective disorder were similar to values obtained in recent studies of adult patients. The results are discussed in relation to historical conceptions of adolescent psychopathology.

An exploratory study on low-concentration hexavalent chromium adsorption by Fe(III)-cross-linked chitosan beads

PubMed Central

Zhang, Yuanjing; Qian, Jin; Xin, Xu; Hu, Sihai; Zhang, Shuai; Wei, Jianguo

2017-01-01

In this study, Fe(III)-cross-linked chitosan beads (Fe(III)-CBs) were synthesized and employed to explore the characteristics and primary mechanism of their hexavalent chromium (Cr(VI)) adsorption under low concentration Cr(VI) (less than 20.0 mg l−1) and a pH range from 2.0 to 8.0. Batch tests were conducted to determine the Cr(VI) adsorption capacity and kinetics, and the effects of pH and temperature on the adsorption under low concentration Cr(VI) and a pH range from 2.0 to 8.0. Scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy were employed to explore the characteristics of Fe(III)-CBs and their Cr(VI) adsorption mechanisms. The results show that, unlike the adsorption of other absorbents, the Cr(VI) adsorption was efficient in a wide pH range from 2.0 to 6.0, and well described by the pseudo-first-order model and the Langmuir–Freundlich isotherm model. The capacity of Cr(VI) adsorption by Fe(III)-CBs was as high as 166.3 mg g−1 under temperature 25°C and pH 6.0. The desorption test was also carried out by 0.1 mol l−1 NaOH solution for Fe(III)-CBs regeneration. It was found that Fe(III)-CBs could be re-used for five adsorption–desorption cycles without significant decrease in Cr(VI) adsorption capacity. Ion exchange was confirmed between functional groups (i.e. amino group) and Cr(VI) anions (i.e. CrO42−). The amino-like functional groups played a key role in Cr(VI) distribution on the Fe(III)-CBs surface; Cr(VI) adsorbed on Fe(III)-CBs was partially reduced to Cr(III) with alcoholic group served as electron donor, and then formed another rate-limiting factor. So, Fe(III)-CBs has a good prospect in purifying low concentration Cr(VI) water with a pH range from 2.0 to 6.0. PMID:29291084

Reliability and Construct Validity of the 6-Minute Racerunner Test in Children and Youth with Cerebral Palsy, GMFCS Levels III and IV.

PubMed

Bolster, Eline A M; Dallmeijer, Annet J; de Wolf, G Sander; Versteegt, Marieke; Schie, Petra E M van

2017-05-01

To determine the test-retest reliability and construct validity of a novel 6-Minute Racerunner Test (6MRT) in children and youth with cerebral palsy (CP) classified as Gross Motor Function Classification System (GMFCS) levels III and IV. The racerunner is a step-propelled tricycle. The participants were 38 children and youth with CP (mean age 11 y 2 m, SD 3 y 7 m; GMFCS III, n = 19; IV, n = 19). Racerunner capability was determined as the distance covered during the 6MRT on three occasions. The intraclass correlation coefficient (ICC), standard error of measurement (SEM), and smallest detectable differences (SDD) were calculated to assess test-retest reliability. The ICC for tests 2 and 3 were 0.89 (SDD 37%; 147 m) for children in level III and 0.91 for children in level IV (SDD 52%; 118 m). When the average of two separate test occasions was used, the SDDs were reduced to 26% (104 m; level III) and 37% (118 m; level IV). For tests 1 to 3, the mean distance covered increased from 345 m (SD 148 m) to 413 m (SD 137 m) for children in level III, and from 193 m (SD 100 m) to 239 m (SD 148 m) for children in level IV. Results suggest high test-retest reliability. However, large SDDs indicate that a single 6MRT measurement is only useful for individual evaluation when large improvements are expected, or when taking the average of two tests. The 6MRT discriminated the distance covered between children and youth in levels III and IV, supporting construct validity.

32 CFR 2003.3 - Functions (Article III).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 32 National Defense 6 2014-07-01 2014-07-01 false Functions (Article III). 2003.3 Section 2003.3 National Defense Other Regulations Relating to National Defense INFORMATION SECURITY OVERSIGHT OFFICE...) BYLAWS, RULES, AND APPEAL PROCEDURES Bylaws § 2003.3 Functions (Article III). In carrying out its purpose...

32 CFR 2003.3 - Functions (Article III).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 32 National Defense 6 2013-07-01 2013-07-01 false Functions (Article III). 2003.3 Section 2003.3 National Defense Other Regulations Relating to National Defense INFORMATION SECURITY OVERSIGHT OFFICE...) BYLAWS, RULES, AND APPEAL PROCEDURES Bylaws § 2003.3 Functions (Article III). In carrying out its purpose...

Effects of gross motor function and manual function levels on performance-based ADL motor skills of children with spastic cerebral palsy.

PubMed

Park, Myoung-Ok

2017-02-01

[Purpose] The purpose of this study was to determine effects of Gross Motor Function Classification System and Manual Ability Classification System levels on performance-based motor skills of children with spastic cerebral palsy. [Subjects and Methods] Twenty-three children with cerebral palsy were included. The Assessment of Motor and Process Skills was used to evaluate performance-based motor skills in daily life. Gross motor function was assessed using Gross Motor Function Classification Systems, and manual function was measured using the Manual Ability Classification System. [Results] Motor skills in daily activities were significantly different on Gross Motor Function Classification System level and Manual Ability Classification System level. According to the results of multiple regression analysis, children categorized as Gross Motor Function Classification System level III scored lower in terms of performance based motor skills than Gross Motor Function Classification System level I children. Also, when analyzed with respect to Manual Ability Classification System level, level II was lower than level I, and level III was lower than level II in terms of performance based motor skills. [Conclusion] The results of this study indicate that performance-based motor skills differ among children categorized based on Gross Motor Function Classification System and Manual Ability Classification System levels of cerebral palsy.

Study on the Effectiveness of Virtual Reality Game-Based Training on Balance and Functional Performance in Individuals with Paraplegia

PubMed Central

Khurana, Meetika; Walia, Shefali

2017-01-01

Objective: To determine whether there is any difference between virtual reality game–based balance training and real-world task-specific balance training in improving sitting balance and functional performance in individuals with paraplegia. Methods: The study was a pre test–post test experimental design. There were 30 participants (28 males, 2 females) with traumatic spinal cord injury randomly assigned to 2 groups (group A and B). The levels of spinal injury of the participants were between T6 and T12. The virtual reality game–based balance training and real-world task-specific balance training were used as interventions in groups A and B, respectively. The total duration of the intervention was 4 weeks, with a frequency of 5 times a week; each training session lasted 45 minutes. The outcome measures were modified Functional Reach Test (mFRT), t-shirt test, and the self-care component of the Spinal Cord Independence Measure–III (SCIM-III). Results: There was a significant difference for time (p = .001) and Time × Group effect (p = .001) in mFRT scores, group effect (p = .05) in t-shirt test scores, and time effect (p = .001) in the self-care component of SCIM-III. Conclusions: Virtual reality game–based training is better in improving balance and functional performance in individuals with paraplegia than real-world task-specific balance training. PMID:29339902

Study on the Effectiveness of Virtual Reality Game-Based Training on Balance and Functional Performance in Individuals with Paraplegia.

PubMed

Khurana, Meetika; Walia, Shefali; Noohu, Majumi M

2017-01-01

Objective: To determine whether there is any difference between virtual reality game-based balance training and real-world task-specific balance training in improving sitting balance and functional performance in individuals with paraplegia. Methods: The study was a pre test-post test experimental design. There were 30 participants (28 males, 2 females) with traumatic spinal cord injury randomly assigned to 2 groups (group A and B). The levels of spinal injury of the participants were between T6 and T12. The virtual reality game-based balance training and real-world task-specific balance training were used as interventions in groups A and B, respectively. The total duration of the intervention was 4 weeks, with a frequency of 5 times a week; each training session lasted 45 minutes. The outcome measures were modified Functional Reach Test (mFRT), t-shirt test, and the self-care component of the Spinal Cord Independence Measure-III (SCIM-III). Results: There was a significant difference for time ( p = .001) and Time × Group effect ( p = .001) in mFRT scores, group effect ( p = .05) in t-shirt test scores, and time effect ( p = .001) in the self-care component of SCIM-III. Conclusions: Virtual reality game-based training is better in improving balance and functional performance in individuals with paraplegia than real-world task-specific balance training.

Global disulfide bond profiling for crude snake venom using dimethyl labeling coupled with mass spectrometry and RADAR algorithm.

PubMed

Huang, Sheng Yu; Chen, Sung Fang; Chen, Chun Hao; Huang, Hsuan Wei; Wu, Wen Guey; Sung, Wang Chou

2014-09-02

Snake venom consists of toxin proteins with multiple disulfide linkages to generate unique structures and biological functions. Determination of these cysteine connections usually requires the purification of each protein followed by structural analysis. In this study, dimethyl labeling coupled with LC-MS/MS and RADAR algorithm was developed to identify the disulfide bonds in crude snake venom. Without any protein separation, the disulfide linkages of several cytotoxins and PLA2 could be solved, including more than 20 disulfide bonds. The results show that this method is capable of analyzing protein mixture. In addition, the approach was also used to compare native cytotoxin 3 (CTX III) and its scrambled isomer, another category of protein mixture, for unknown disulfide bonds. Two disulfide-linked peptides were observed in the native CTX III, and 10 in its scrambled form, X-CTX III. This is the first study that reports a platform for the global cysteine connection analysis on a protein mixture. The proposed method is simple and automatic, offering an efficient tool for structural and functional studies of venom proteins.

Fructose bisphosphate aldolase is involved in the control of RNA polymerase III-directed transcription.

PubMed

Cieśla, Małgorzata; Mierzejewska, Jolanta; Adamczyk, Małgorzata; Farrants, Ann-Kristin Östlund; Boguta, Magdalena

2014-06-01

Yeast Fba1 (fructose 1,6-bisphosphate aldolase) is a glycolytic enzyme essential for viability. The overproduction of Fba1 enables overcoming of a severe growth defect caused by a missense mutation rpc128-1007 in a gene encoding the C128 protein, the second largest subunit of the RNA polymerase III complex. The suppression of the growth phenotype by Fba1 is accompanied by enhanced de novo tRNA transcription in rpc128-1007 cells. We inactivated residues critical for the catalytic activity of Fba1. Overproduction of inactive aldolase still suppressed the rpc128-1007 phenotype, indicating that the function of this glycolytic enzyme in RNA polymerase III transcription is independent of its catalytic activity. Yeast Fba1 was determined to interact with the RNA polymerase III complex by coimmunoprecipitation. Additionally, a role of aldolase in control of tRNA transcription was confirmed by ChIP experiments. The results indicate a novel direct relationship between RNA polymerase III transcription and aldolase. Copyright © 2014 Elsevier B.V. All rights reserved.

26 CFR 301.7701(i)-4 - Special rules for certain entities.

Code of Federal Regulations, 2011 CFR

2011-04-01

... the debt obligations in the performance of a governmental purpose; and (iii) The entity holds the... packaging of debt obligations for re-sale on the secondary market even if any profits from the sale are used in the performance of an essential governmental function. (3) Determinations by the Commissioner. If...

7 CFR 4290.1620 - Functions of agents, including Central Registration Agent, Selling Agent and Fiscal Agent.

Code of Federal Regulations, 2010 CFR

2010-01-01

... Debentures and/or TCs. (iv) Arranging for the production of Offering Circulars, certificates, and such other... to determine those factors that will minimize or reduce the cost of funding Debentures. (iii) Monitor... the Secretary; (vii) Remain custodian of such other documentation as the Secretary shall direct by...

Functional Requirements: 2014 No Child Left Behind--Annual Measurable Achievement Objectives

ERIC Educational Resources Information Center

Minnesota Department of Education, 2014

2014-01-01

This document describes the Minnesota No Child Left Behind (NCLB) calculation as it relates to measuring Title III districts for Annual Measurable Achievement Objectives (AMAO). In 2012, a new assessment was used to measure language proficiency skills for English Learners. New AMAO targets were created, and new values for determining individual…

Effects of molecular composition of natural organic matter on ferric iron complexation at circumneutral pH.

PubMed

Fujii, Manabu; Imaoka, Akira; Yoshimura, Chihiro; Waite, T D

2014-04-15

Thermodynamic and kinetic parameters for ferric iron (Fe[III]) complexation by well-characterized humic substances (HS) from various origins were determined by a competitive ligand method with 5-sulfosalicylic acid at circumneutral pH (6.0-8.0) and an ionic strength of ∼0.06 M. The measured Fe binding properties including conditional stability constants and complexation capacities ranged over more than 2 orders of magnitude, depending on the origin and the particular operationally defined fraction of HS examined. Statistical comparison of the complexation parameters to a range of chemical properties of the HS indicated a strong positive correlation between Fe(III) complexation capacity and aromatic carbon content in the HS at all pHs examined. In contrast, the complexation capacity was determined to be up to a few orders of magnitude smaller than the concentration of carboxylic and phenolic groups present. Therefore, specific functional groups including those resident in the proximity of aromatic structures within the HS are likely preferable for Fe(III) coordination under the conditions examined. Overall, our results suggest that the concentration of dissolved Fe(III) complexes in natural waters is substantially influenced by variation in HS characteristics in addition to other well-known factors such as HS concentration and nature and concentration of competing cations present.

A Novel Sensor for Monitoring of Iron(III) Ions Based on Porphyrins

PubMed Central

Vlascici, Dana; Fagadar-Cosma, Eugenia; Popa, Iuliana; Chiriac, Vlad; Gil-Agusti, Mayte

2012-01-01

Three A3B porphyrins with mixed carboxy-, phenoxy-, pyridyl-, and dimethoxy-substituent functionalization on the meso-phenyl groups were obtained by multicomponent synthesis, fully characterized and used as ionophores for preparing PVC-based membrane sensors selective to iron(III). The membranes have an ionophore:PVC:plasticizer composition ratio of 1:33:66. Sodium tetraphenylborate was used as additive (20 mol% relative to ionophore). The performance characteristics (linear concentration range, slope and selectivity) of the sensors were investigated. The best results were obtained for the membrane based on 5-(4-carboxyphenyl)-10,15,20-tris(4-phenoxyphenyl)-porphyrin plasticized with bis(2-ethylhexyl)sebacate, in a linear range from 1 × 10−7–1 × 10−1 M with a slope of 21.6 mV/decade. The electrode showed high selectivity with respect to alkaline and heavy metal ions and a response time of 20 s. The influence of pH on the sensor response was studied. The sensor was used for a period of six weeks and the utility has been tested for the quantitative determination of Fe(III) in recovered solutions from spent lithium ion batteries and for the quantitative determination of Fe(III) in tap water samples. PMID:22969395

Dye Oriza sativa glutinosa doped Fe as a active element of Dye Sensitized Solar Cell (DSSC)

NASA Astrophysics Data System (ADS)

Prasada, A. B.; Fadli, U. M.; Cari; Supriyanto, A.

2016-11-01

The aims of the research are to determine the effect of doping Fe (III) Sulphate into dye Oriza sativa glutinosa on the characteristics parameters of solar cells, to determine the optical characteristic, functional group and electrical characteristic of dye Oriza sativa glutinosa doped Fe (III) sulphate. TiO2 nano size as much as 0.5 gr dissolved in 3 ml ethanol. 100 gr black sticky rice (Oriza sativa glutinosa) was immersed in 80 ml ethanol solution (95%) and kept at room temperature without exposing to light. Then it was filtered with a filter paper no.42, and the extracted result was process with chromatography. Furthermore, it was doped with Fe (III) sulphate respectively of 10-1 M, 10-2 M, 10-3 M. The characteristic of dye solution was measured using UV-Visible Spectrophotometer Lambda 25 for absorbance, Elkahfi 100/I-V meter for conductivity amd Keithey 2602A for characterization of current and voltage (I-V). The result showed that the area of dye Oriza sativa glutionosa doped Fe (III) sulphate with concentration 10-1 M the largest, because the value of Voc intercept at 6.40 × 10-1 mV and the value Isc intercept at 1.89 × 10-3 mA, with efficiency value is 0.148%.

[Comparison of the Wechsler Memory Scale-III and the Spain-Complutense Verbal Learning Test in acquired brain injury: construct validity and ecological validity].

PubMed

Luna-Lario, P; Pena, J; Ojeda, N

2017-04-16

To perform an in-depth examination of the construct validity and the ecological validity of the Wechsler Memory Scale-III (WMS-III) and the Spain-Complutense Verbal Learning Test (TAVEC). The sample consists of 106 adults with acquired brain injury who were treated in the Area of Neuropsychology and Neuropsychiatry of the Complejo Hospitalario de Navarra and displayed memory deficit as the main sequela, measured by means of specific memory tests. The construct validity is determined by examining the tasks required in each test over the basic theoretical models, comparing the performance according to the parameters offered by the tests, contrasting the severity indices of each test and analysing their convergence. The external validity is explored through the correlation between the tests and by using regression models. According to the results obtained, both the WMS-III and the TAVEC have construct validity. The TAVEC is more sensitive and captures not only the deficits in mnemonic consolidation, but also in the executive functions involved in memory. The working memory index of the WMS-III is useful for predicting the return to work at two years after the acquired brain injury, but none of the instruments anticipates the disability and dependence at least six months after the injury. We reflect upon the construct validity of the tests and their insufficient capacity to predict functionality when the sequelae become chronic.

The mechanism of transition-metal (Cu or Pd)-catalyzed synthesis of benzimidazoles from amidines: theoretical investigation.

PubMed

Li, Juan; Gu, Honghong; Wu, Caihong; Du, Lijuan

2014-11-28

In this study, the Cu(OAc)2- and [PdCl2(PhCN)2]-catalyzed syntheses of benzimidazoles from amidines were theoretically investigated using density functional theory calculations. For the Cu-catalyzed system, our calculations supported a four-step-pathway involving C-H activation of an arene with Cu(II) via concerted metalation-deprotonation (CMD), followed by oxidation of the Cu(II) intermediate and deprotonation of the imino group by Cu(III), and finally reductive elimination from Cu(III). In our calculations, the barriers for the CMD step and the oxidation step are the same. The results are different from the ones reported by Fu et al. in which the whole reaction mechanism includes three steps and the CMD step is rate determining. On the basis of the calculation results for the [PdCl2(PhCN)2]-catalyzed system, C-H bond breaking by CMD occurs first, followed by the rate-determining C-N bond formation and N-H deprotonation. Pd(III) species is not involved in the [PdCl2(PhCN)2]-catalyzed syntheses of benzimidazoles from amidines.

Systematic theoretical investigation of the zero-field splitting in Gd(III) complexes: Wave function and density functional approaches

NASA Astrophysics Data System (ADS)

Khan, Shehryar; Kubica-Misztal, Aleksandra; Kruk, Danuta; Kowalewski, Jozef; Odelius, Michael

2015-01-01

The zero-field splitting (ZFS) of the electronic ground state in paramagnetic ions is a sensitive probe of the variations in the electronic and molecular structure with an impact on fields ranging from fundamental physical chemistry to medical applications. A detailed analysis of the ZFS in a series of symmetric Gd(III) complexes is presented in order to establish the applicability and accuracy of computational methods using multiconfigurational complete-active-space self-consistent field wave functions and of density functional theory calculations. The various computational schemes are then applied to larger complexes Gd(III)DOTA(H2O)-, Gd(III)DTPA(H2O)2-, and Gd(III)(H2O)83+ in order to analyze how the theoretical results compare to experimentally derived parameters. In contrast to approximations based on density functional theory, the multiconfigurational methods produce results for the ZFS of Gd(III) complexes on the correct order of magnitude.

Combined time-resolved laser fluorescence spectroscopy and extended X-ray absorption fine structure spectroscopy study on the complexation of trivalent actinides with chloride at T = 25-200 °C.

PubMed

Skerencak-Frech, Andrej; Fröhlich, Daniel R; Rothe, Jörg; Dardenne, Kathy; Panak, Petra J

2014-01-21

The complexation of trivalent actinides (An(III)) with chloride is studied in the temperature range from 25 to 200 °C by spectroscopic methods. Time-resolved laser fluorescence spectroscopy (TRLFS) is applied to determine the thermodynamic data of Cm(III)-Cl(-) complexes, while extended X-ray absorption fine structure spectroscopy (EXAFS) is used to determine the structural data of the respective Am(III) complexes. The experiments are performed in a custom-built high-temperature cell which is modified for the respective spectroscopic technique. The TRLFS results show that at 25 °C the speciation is dominated mainly by the Cm(3+) aquo ion. Only a minor fraction of the CmCl(2+) complex is present in solution. As the temperature increases, the fraction of this species decreases further. Simultaneously, the fraction of the CmCl2(+) complex increases strongly with the temperature. Also, the CmCl3 complex is formed to a minor extent at T > 160 °C. The conditional stability constant log β'2 is determined as a function of the temperature and extrapolated to zero ionic strength with the specific ion interaction theory approach. The log β°2(T) values increase by more than 3 orders of magnitude in the studied temperature range. The temperature dependency of log β°2 is fitted by the extended van't Hoff equation to determine ΔrH°m, ΔrS°m, and ΔrC°p,m. The EXAFS results support these findings. The results confirm the absence of americium(III) chloride complexes at T = 25 and 90 °C ([Am(III)] = 10(-3) m, [Cl(-)] = 3.0 m), and the spectra are described by 9-10 oxygen atoms at a distance of 2.44-2.48 Å. At T = 200 °C two chloride ligands are present in the inner coordination sphere of Am(III) at a distance of 2.78 Å.

Patient satisfaction after open reduction and internal fixation through lateral extensile approach in displaced intraarticular calcaneal fractures (Sander's type II and III).

PubMed

Kavin, Khatri; Vijay, Sharma; Devendra, Lakhotia; Kamran, Farooque

2016-01-01

To determine patient satisfaction in the patients of displaced intraarticular calcaneal fractures treated with standard lateral approach. The patients of displaced calcaneal fractures (Sander's type II and III) treated between March 2009 and March 2012 were included in the retrospective review and functional outcome was evaluated using American Orthopaedic Foot and Ankle Society (AOFAS) hind foot score, Creighton Nebraska Health Foundation Assessment (CNHFA) scale and foot function index (FFI). The cohort included 26 patients (19 males: seven were females) with a mean age of 38.16 ± 13.53 years (range 18-64 years). The mean period of follow-up was 24.42 ± 6.68 months. The patients achieved good functional scores after anatomical reduction of the fracture. The complication rate was low following strict inclusion criteria. Careful patient selection in displaced intraarticular calcaneal fractures treated through lateral extensile approach achieves good patient satisfaction.

N-butylamine functionalized graphene oxide for detection of iron(III) by photoluminescence quenching.

PubMed

Gholami, Javad; Manteghian, Mehrdad; Badiei, Alireza; Ueda, Hiroshi; Javanbakht, Mehran

2016-02-01

An N-butylamine functionalized graphene oxide nanolayer was synthesized and characterized by ultraviolet (UV)-visible spectrometry, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy. Detection of iron(III) based on photoluminescence spectroscopy was investigated. The N-butylamine functionalized graphene oxide was shown to specifically interact with iron (III), compared with other cationic trace elements including potassium (I), sodium (I), calcium (II), chromium (III), zinc (II), cobalt (II), copper (II), magnesium (II), manganese (II), and molybdenum (VI). The quenching effect of iron (III) on the luminescence emission of N-butylamine functionalized graphene oxide layer was used to detect iron (III). The limit of detection (2.8 × 10(-6)  M) and limit of quantitation (2.9 × 10(-5)  M) were obtained under optimal conditions. Copyright © 2015 John Wiley & Sons, Ltd.

Capturing Chromosome Conformation

NASA Astrophysics Data System (ADS)

Dekker, Job; Rippe, Karsten; Dekker, Martijn; Kleckner, Nancy

2002-02-01

We describe an approach to detect the frequency of interaction between any two genomic loci. Generation of a matrix of interaction frequencies between sites on the same or different chromosomes reveals their relative spatial disposition and provides information about the physical properties of the chromatin fiber. This methodology can be applied to the spatial organization of entire genomes in organisms from bacteria to human. Using the yeast Saccharomyces cerevisiae, we could confirm known qualitative features of chromosome organization within the nucleus and dynamic changes in that organization during meiosis. We also analyzed yeast chromosome III at the G1 stage of the cell cycle. We found that chromatin is highly flexible throughout. Furthermore, functionally distinct AT- and GC-rich domains were found to exhibit different conformations, and a population-average 3D model of chromosome III could be determined. Chromosome III emerges as a contorted ring.

Density functional theory calculations of III-N based semiconductors with mBJLDA

NASA Astrophysics Data System (ADS)

Gürel, Hikmet Hakan; Akıncı, Özden; Ünlü, Hilmi

2017-02-01

In this work, we present first principles calculations based on a full potential linear augmented plane-wave method (FP-LAPW) to calculate structural and electronic properties of III-V based nitrides such as GaN, AlN, InN in a zinc-blende cubic structure. First principles calculation using the local density approximation (LDA) and generalized gradient approximation (GGA) underestimate the band gap. We proposed a new potential called modified Becke-Johnson local density approximation (MBJLDA) that combines modified Becke-Johnson exchange potential and the LDA correlation potential to get better band gap results compared to experiment. We compared various exchange-correlation potentials (LSDA, GGA, HSE, and MBJLDA) to determine band gaps and structural properties of semiconductors. We show that using MBJLDA density potential gives a better agreement with experimental data for band gaps III-V nitrides based semiconductors.

Removal of hexavalent Cr by coconut coir and derived chars--the effect of surface functionality.

PubMed

Shen, Ying-Shuian; Wang, Shan-Li; Tzou, Yu-Min; Yan, Ya-Yi; Kuan, Wen-Hui

2012-01-01

The Cr(VI) removal by coconut coir (CC) and chars obtained at various pyrolysis temperatures were evaluated. Increasing the pyrolysis temperature resulted in an increased surface area of the chars, while the corresponding content of oxygen-containing functional groups of the chars decreased. The Cr(VI) removal by CC and CC-derived chars was primarily attributed to the reduction of Cr(VI) to Cr(III) by the materials and the extent and rate of the Cr(VI) reduction were determined by the oxygen-containing functional groups in the materials. The contribution of pure Cr(VI) adsorption to the overall Cr(VI) removal became relatively significant for the chars obtained at higher temperatures. Accordingly, to develop a cost-effective method for removing Cr(VI) from water, the original CC is more advantageous than the carbonaceous counterparts because no pyrolysis is required for the application and CC has a higher content of functional groups for reducing Cr(VI) to less toxic Cr(III). Copyright © 2011 Elsevier Ltd. All rights reserved.

Quantification of functional abilities in Rett syndrome: a comparison between stages III and IV

PubMed Central

Monteiro, Carlos BM; Savelsbergh, Geert JP; Smorenburg, Ana RP; Graciani, Zodja; Torriani-Pasin, Camila; de Abreu, Luiz Carlos; Valenti, Vitor E; Kok, Fernando

2014-01-01

We aimed to evaluate the functional abilities of persons with Rett syndrome (RTT) in stages III and IV. The group consisted of 60 females who had been diagnosed with RTT: 38 in stage III, mean age (years) of 9.14, with a standard deviation of 5.84 (minimum 2.2/maximum 26.4); and 22 in stage IV, mean age of 12.45, with a standard deviation of 6.17 (minimum 5.3/maximum 26.9). The evaluation was made using the Pediatric Evaluation of Disability Inventory, which has 197 items in the areas of self-care, mobility, and social function. The results showed that in the area of self-care, stage III and stage IV RTT persons had a level of 24.12 and 18.36 (P=0.002), respectively. In the area of mobility, stage III had 37.22 and stage IV had 14.64 (P<0.001), while in the area of social function, stage III had 17.72 and stage IV had 12.14 (P=0.016). In conclusion, although persons with stage III RTT have better functional abilities when compared with stage IV, the areas of mobility, self-care, and social function are quite affected, which shows a great functional dependency and need for help in basic activities of daily life. PMID:25061307

Optimization of vehicle deceleration to reduce occupant injury risks in frontal impact.

PubMed

Mizuno, Koji; Itakura, Takuya; Hirabayashi, Satoko; Tanaka, Eiichi; Ito, Daisuke

2014-01-01

In vehicle frontal impacts, vehicle acceleration has a large effect on occupant loadings and injury risks. In this research, an optimal vehicle crash pulse was determined systematically to reduce injury measures of rear seat occupants by using mathematical simulations. The vehicle crash pulse was optimized based on a vehicle deceleration-deformation diagram under the conditions that the initial velocity and the maximum vehicle deformation were constant. Initially, a spring-mass model was used to understand the fundamental parameters for optimization. In order to investigate the optimization under a more realistic situation, the vehicle crash pulse was also optimized using a multibody model of a Hybrid III dummy seated in the rear seat for the objective functions of chest acceleration and chest deflection. A sled test using a Hybrid III dummy was carried out to confirm the simulation results. Finally, the optimal crash pulses determined from the multibody simulation were applied to a human finite element (FE) model. The optimized crash pulse to minimize the occupant deceleration had a concave shape: a high deceleration in the initial phase, low in the middle phase, and high again in the final phase. This crash pulse shape depended on the occupant restraint stiffness. The optimized crash pulse determined from the multibody simulation was comparable to that from the spring-mass model. From the sled test, it was demonstrated that the optimized crash pulse was effective for the reduction of chest acceleration. The crash pulse was also optimized for the objective function of chest deflection. The optimized crash pulse in the final phase was lower than that obtained for the minimization of chest acceleration. In the FE analysis of the human FE model, the optimized pulse for the objective function of the Hybrid III chest deflection was effective in reducing rib fracture risks. The optimized crash pulse has a concave shape and is dependent on the occupant restraint stiffness and maximum vehicle deformation. The shapes of the optimized crash pulse in the final phase were different for the objective functions of chest acceleration and chest deflection due to the inertial forces of the head and upper extremities. From the human FE model analysis it was found that the optimized crash pulse for the Hybrid III chest deflection can substantially reduce the risk of rib cage fractures. Supplemental materials are available for this article. Go to the publisher's online edition of Traffic Injury Prevention to view the supplemental file.

Adsorption of transition metal ions from aqueous solutions onto a novel silica gel matrix inorganic-organic composite material.

PubMed

Yin, Ping; Xu, Qiang; Qu, Rongjun; Zhao, Guifang; Sun, Yanzhi

2010-01-15

A novel inorganic-organic composite material silica gel microspheres encapsulated by imidazole functionalized polystyrene (SG-PS-azo-IM) has been synthesized and characterized. This composite material was used to investigate the adsorption of Cr(III), Mn(II), Fe(III), Ni(II), Cu(II), Zn(II), Hg(II), Pb(II), Pd(II), Pt(II), Ag(I), and Au(III) from aqueous solutions, and the research results displayed that SG-PS-azo-IM has the highest adsorption capacity for Au(III). Langmuir and Freundlich isotherm models were applied to analyze the experimental data, the best interpretation for the experimental data was given by the Langmuir isotherm equation, and the maximum adsorption capacity for Au(III) is 1.700 mmol/g. The adsorption selectivity, the dynamic adsorption and desorption properties of SG-PS-azo-IM for Au(III) have also been studied. The results showed that SG-PS-azo-IM had excellent adsorption for Au(III) in four binary ions system, especially in the systems of Au(III)-Zn(II) and Au(III)-Cu(II), and almost Au(III) could be desorbed with the eluent solution of 0.5% thiourea in 1 mol/L HCl. Moreover, this novel composite material was used to preconcentrate Au(III) before its determination by flame atomic adsorption spectrometry. In the initial concentration range of 0.10-0.20 microg/mL, multiple of enrichment could reach 5.28. Thus, silica gel encapsulated by polystyrene coupling with imidazole (SG-PS-azo-IM) is favorable and useful for the removal of transition metal ions, and the high adsorption capacity makes it a good promising candidate material for Au(III) removal.

The impact of mixed solvents on the complexation thermodynamics of Eu(III) by simple carboxylate and amino carboxylate ligands

DOE PAGES

Felmy, Heather M.; Bennett, Kevin T.; Clark, Sue B.

2017-05-12

To gain insight on the role of mixed solvents on the thermodynamic driving forces for the complexation between trivalent f-elements and organic ligands, solution phase thermodynamic parameters were determined for Eu(III) complexation with 2-hydroxyisobutyric acid (HIBA) and 2-aminoisobutyric acid (AIBA) in mixed methanol (MeOH)-water and N,N-dimethylformamide (DMF)-water solvents. Included in this study were the determination of mixed solvent autoprotolysis constants (pK α) as well as the thermodynamic formation constants: log β, ΔG, ΔH, and ΔS, for ligand protonation and Eu(III)-ligand complexation utilizing potentiometry and calorimetry techniques. The results presented are conditional thermodynamic values determined at an ionic strength of 1.0more » M NaClO 4 and a temperature of 298 K. It was found that moving from an aqueous solution to a binary aqueous-organic solvent affected all solution equilibria to some degree and that the extent of change depended on both the type of mixed solvent and the ligand in each study. Here, the ability to understand and predict these changes in thermodynamic values as a function of solvent composition provides important information about the chemistry of the trivalent f-elements.« less

The impact of mixed solvents on the complexation thermodynamics of Eu(III) by simple carboxylate and amino carboxylate ligands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Felmy, Heather M.; Bennett, Kevin T.; Clark, Sue B.

To gain insight on the role of mixed solvents on the thermodynamic driving forces for the complexation between trivalent f-elements and organic ligands, solution phase thermodynamic parameters were determined for Eu(III) complexation with 2-hydroxyisobutyric acid (HIBA) and 2-aminoisobutyric acid (AIBA) in mixed methanol (MeOH)-water and N,N-dimethylformamide (DMF)-water solvents. Included in this study were the determination of mixed solvent autoprotolysis constants (pK α) as well as the thermodynamic formation constants: log β, ΔG, ΔH, and ΔS, for ligand protonation and Eu(III)-ligand complexation utilizing potentiometry and calorimetry techniques. The results presented are conditional thermodynamic values determined at an ionic strength of 1.0more » M NaClO 4 and a temperature of 298 K. It was found that moving from an aqueous solution to a binary aqueous-organic solvent affected all solution equilibria to some degree and that the extent of change depended on both the type of mixed solvent and the ligand in each study. Here, the ability to understand and predict these changes in thermodynamic values as a function of solvent composition provides important information about the chemistry of the trivalent f-elements.« less

1-(2-Formamidoethyl)-3-phenylurea functionalized activated carbon for selective solid-phase extraction and preconcentration of metal ions.

PubMed

Tu, Zhifeng; He, Qun; Chang, Xijun; Hu, Zheng; Gao, Ru; Zhang, Lina; Li, Zhenhua

2009-09-07

A novel method that utilizes 1-(2-formamidoethyl)-3-phenylurea-modified activated carbon (AC-1-(2-formamidoethyl)-3-phenylurea) as a solid-phase extractant has been developed for simultaneous preconcentration of trace Cr(III), Cu(II), Fe(III) and Pb(II) prior to the measurement by inductively coupled plasma atomic emission spectrometry (ICP-AES). Experimental conditions for effective adsorption of trace levels of Cr(III), Cu(II), Fe(III) and Pb(II) were optimized using batch and column procedures in detail. The optimum pH value for the separation of metal ions simultaneously on the new sorbent was 4. And the adsorbed metal ions could be completely eluted by using 2.0 mL 2.0 mol L(-1) HCl solution. Common coexisting ions did not interfere with the separation and determination of target metal ions. The maximum static adsorption capacity of the sorbent at optimum conditions was found to be 39.8, 39.9, 77.8 and 17.3 mg g(-1) for Cr(III), Cu(II), Fe(III) and Pb(II), respectively. The detection limits of the method were found to be 0.15, 0.41, 0.27 and 0.36 ng mL(-1) for Cr(III), Cu(II), Fe(III) and Pb(II), respectively. The relative standard deviation (RSD) of the method was lower than 4.0% (n=8). The method was successfully applied for the preconcentration of trace Cr(III), Cu(II), Fe(III) and Pb(II) in natural and certified samples with satisfactory results.

A Guide to Computer Simulations of Three Adaptive Instructional Models for the Advanced Instructional System Phases II and III. Final Report.

ERIC Educational Resources Information Center

Hansen, Duncan N.; And Others

Computer simulations of three individualized adaptive instructional models (AIM) were undertaken to determine if these models function as prescribed in Air Force technical training programs. In addition, the project sought to develop a user's guide for effective understanding of adaptive models during field implementation. Successful simulations…

Genomic binding profiles of functionally distinct RNA polymerase III transcription complexes in human cells.

PubMed

Moqtaderi, Zarmik; Wang, Jie; Raha, Debasish; White, Robert J; Snyder, Michael; Weng, Zhiping; Struhl, Kevin

2010-05-01

Genome-wide occupancy profiles of five components of the RNA polymerase III (Pol III) machinery in human cells identified the expected tRNA and noncoding RNA targets and revealed many additional Pol III-associated loci, mostly near short interspersed elements (SINEs). Several genes are targets of an alternative transcription factor IIIB (TFIIIB) containing Brf2 instead of Brf1 and have extremely low levels of TFIIIC. Strikingly, expressed Pol III genes, unlike nonexpressed Pol III genes, are situated in regions with a pattern of histone modifications associated with functional Pol II promoters. TFIIIC alone associates with numerous ETC loci, via the B box or a novel motif. ETCs are often near CTCF binding sites, suggesting a potential role in chromosome organization. Our results suggest that human Pol III complexes associate preferentially with regions near functional Pol II promoters and that TFIIIC-mediated recruitment of TFIIIB is regulated in a locus-specific manner.

Genomic Binding Profiles of Functionally Distinct RNA Polymerase III Transcription Complexes in Human Cells

PubMed Central

Moqtaderi, Zarmik; Wang, Jie; Raha, Debasish; White, Robert J.; Snyder, Michael; Weng, Zhiping; Struhl, Kevin

2012-01-01

Genome-wide occupancy profiles of five components of the RNA Polymerase III (Pol III) machinery in human cells identified the expected tRNA and non-coding RNA targets and revealed many additional Pol III-associated loci, mostly near SINEs. Several genes are targets of an alternative TFIIIB containing Brf2 instead of Brf1 and have extremely low levels of TFIIIC. Strikingly, expressed Pol III genes, unlike non-expressed Pol III genes, are situated in regions with a pattern of histone modifications associated with functional Pol II promoters. TFIIIC alone associates with numerous ETC loci, via the B box or a novel motif. ETCs are often near CTCF binding sites, suggesting a potential role in chromosome organization. Our results suggest that human Pol III complexes associate preferentially with regions near functional Pol II promoters and that TFIIIC-mediated recruitment of TFIIIB is regulated in a locus-specific manner. PMID:20418883

Change in mobility function and its causes in adults with cerebral palsy by Gross Motor Function Classification System level: A cross-sectional questionnaire study.

PubMed

Himuro, Nobuaki; Mishima, Reiko; Seshimo, Takashi; Morishima, Toshibumi; Kosaki, Keisuke; Ibe, Shigeharu; Asagai, Yoshimi; Minematsu, Koji; Kurita, Kazuhiro; Okayasu, Tsutomu; Shimura, Tsukasa; Hoshino, Kotaro; Suzuki, Toshiro; Yanagizono, Taiichiro

2018-04-07

The prognosis for mobility function by Gross Motor Function Classification System (GMFCS) level is vital as a guide to rehabilitation for people with cerebral palsy. This study sought to investigate change in mobility function and its causes in adults with cerebral palsy by GMFCS level. We conducted a cross-sectional questionnaire study. A total of 386 participants (26 y 8 m, SD 5 y 10 m) with cerebral palsy were analyzed. Participant numbers by GMFCS level were: I (53), II (139), III (74) and IV (120). The median age of participants with peak mobility function in GMFCS level III was younger than that in the other levels. 48% had experienced a decline in mobility. A Kaplan-Meier plot showed the risk of mobility decline increased in GMFCS level III; the hazard ratio was 1.97 (95% CI, 1.20-3.23) compared with level I. The frequently reported causes of mobility decline were changes in environment, and illness and injury in GMFCS level III, stiffness and deformity in level IV, and reduced physical activity in level II and III. Peak mobility function and mobility decline occurred at a younger age in GMFCS level III, with the cause of mobility decline differing by GMFCS level.

Analysis of the Structures and Properties of (GaSb)n (n = 4-9) Clusters through Density Functional Theory.

PubMed

Lu, Qi Liang; Luo, Qi Quan; Huang, Shou Guo; Li, Yi De; Wan, Jian Guo

2016-07-07

An optimization strategy combining global semiempirical quantum mechanical search with all-electron density functional theory was adopted to determine the lowest energy structure of (GaSb)n clusters up to n = 9. The growth pattern of the clusters differed from those of previously reported group III-V binary clusters. A cagelike configuration was found for cluster sizes n ≤ 7. The structure of (GaSb)6 deviated from that of other III-V clusters. Competition existed between core-shell and hollow cage structures of (GaSb)7. Novel noncagelike structures were energetically preferred over the cages for the (GaSb)8 and (GaSb)9 clusters. Electronic properties, such as vertical ionization potential, adiabatic electron affinities, HOMO-LUMO gaps, and average on-site charges on Ga or Sb atoms, as well as binding energies, were computed.

Oral Rehabilitation With Orthognathic Surgery After Dental Implant Placement for Class III Malocclusion With Skeletal Asymmetry and Posterior Bite Collapse.

PubMed

Ohba, Seigo; Nakatani, Yuya; Kawasaki, Takako; Tajima, Nobutaka; Tobita, Takayoshi; Yoshida, Noriaki; Sawase, Takashi; Asahina, Izumi

2015-08-01

Increasing numbers of older patients are seeking orthognathic surgery to treat jaw deformity. However, orthodontic and orthognathic surgical treatment is difficult in cases without occlusal vertical stop. A 55-year-old man presented with Class III malocclusion and mandibular protrusion including esthetic problems and posterior bite collapse. He underwent dental implant treatment to reconstruct an occlusal vertical stop before orthognathic surgery. His occlusal function and esthetic problems improved after surgery, and his skeletal and occlusal stability has been maintained for 6 years. Dental implant placement at appropriate positions could help to determine the position of the proximal segment at orthognathic surgery and could shorten the time required to restore esthetic and occlusal function. This case demonstrates how skeletal and dental stability can be maintained long after surgery in a patient with jaw deformity and posterior bite collapse.

Water Dimers in the Atmosphere II: Results from the VRT(ASP-W)III Potential Surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goldman, N; Saykally, R J; Leforestier, C

We report refined results for the equilibrium constant for water dimerization (K{sub P}), computed as a function of temperature via fully-coupled 6-D calculation of the canonical (H{sub 2}O){sub 2} partition function on VRT(ASP-W)III, the most accurate water dimer potential energy surface currently available. Partial pressure isotherms calculated for a range of temperatures and relative humidities indicate that water dimers can exist in sufficient concentrations (e.g., 10{sup 18}m{sup -3} at 30 C and 100% relative humidity) to affect physical and chemical processes in the atmosphere. The determinations of additional thermodynamic properties ({Delta}G, {Delta}H, {Delta}S, C{sub P}, C{sub V}) for (H{sub 2}O){submore » 2} are presented, and the role of quasi-bound states in the calculation of K{sub P} is discussed at length.« less

The Effect of Pressure and Temperature on Separation of Free Gadolinium(III) From Gd-DTPA Complex by Nanofiltration-Complexation Method

NASA Astrophysics Data System (ADS)

Rahayu, Iman; Anggraeni, Anni; Ukun, MSS; Bahti, Husein H.

2017-05-01

Nowdays, the utilization of rare earth elements has been carried out widely in industry and medicine, one of them is gadolinium in Gd-DTPA complex is used as a contrast agent in a magnetic resonance imaging (MRI) diagnostic to increase the visual contrast between normal tissue and diseased. Although the stability of a given complex may be high enough, the complexation step couldnot have been completed, so there is possible to gadolinium(III) in the complex compound. Therefore, the function of that compounds should be dangerous because of the toxicity of gadolinium(III) in human body. So, it is necessarry to separate free gadolinium(III) from Gd-DTPA complex by nanofiltration-complexation. The method of this study is complexing of Gd2O3 with DTPA ligand by reflux and separation of Gd-DTPA complex from gadolinium(III) with a nanofiltration membrane on the variation of pressures(2, 3, 4, 5, 6 bars) and temperature (25, 30, 35, 40 °C) and determined the flux and rejection. The results of this study are the higher of pressures and temperatures, permeation flux are increasing and ion rejections are decreasing and gave the free gadolinium(III) rejection until 86.26%.

Expression of arsenic resistance genes in the obligate anaerobe Bacteroides vulgatus ATCC 8482, a gut microbiome bacterium

PubMed Central

Li, Jiaojiao; Mandal, Goutam; Rosen, Barry P.

2016-01-01

The response of the obligate anaerobe Bacteroides vulgatus ATCC 8482, a common human gut microbiota, to arsenic was determined. B. vulgatus ATCC 8482 is highly resistant to pentavalent As(V) and methylarsenate (MAs(V)). It is somewhat more sensitive to trivalent inorganic As(III) but 100-fold more sensitive to methylarsenite (MAs(III)) than to As(III). B. vulgatus ATCC 8482 has eight continuous genes in its genome that we demonstrate form an arsenical-inducible transcriptional unit. The first gene of this ars operon, arsR, encodes a putative ArsR As(III)-responsive transcriptional repressor. The next three genes encode proteins of unknown function. The remaining genes, arsDABC, have well-characterized roles in detoxification of inorganic arsenic, but there are no known genes for MAs(III) resistance. Expression of each gene after exposure to trivalent and pentavalent inorganic and methylarsenicals was analyzed. MAs(III) was the most effective inducer. The arsD gene was the most highly expressed of the ars operon genes. These results demonstrate that this anaerobic microbiome bacterium has arsenic-responsive genes that confer resistance to inorganic arsenic and may be responsible for the organism's ability to maintain its prevalence in the gut following dietary exposure to inorganic arsenic. PMID:27040269

Corynebacterium glutamicum MTCC 2745 immobilized on granular activated carbon/MnFe2O4 composite: A novel biosorbent for removal of As(III) and As(V) ions

NASA Astrophysics Data System (ADS)

Podder, M. S.; Majumder, C. B.

2016-11-01

The optimization of biosorption/bioaccumulation process of both As(III) and As(V) has been investigated by using the biosorbent; biofilm of Corynebacterium glutamicum MTCC 2745 supported on granular activated carbon/MnFe2O4 composite (MGAC). The presence of functional groups on the cell wall surface of the biomass that may interact with the metal ions was proved by FT-IR. To determine the most appropriate correlation for the equilibrium curves employing the procedure of the non-linear regression for curve fitting analysis, isotherm studies were performed for As(III) and As(V) using 30 isotherm models. The pattern of biosorption/bioaccumulation fitted well with Vieth-Sladek isotherm model for As(III) and Brouers-Sotolongo and Fritz-Schlunder-V isotherm models for As(V). The maximum biosorption/bioaccumulation capacity estimated using Langmuir model were 2584.668 mg/g for As(III) and 2651.675 mg/g for As(V) at 30 °C temperature and 220 min contact time. The results showed that As(III) and As(V) removal was strongly pH-dependent with an optimum pH value of 7.0. D-R isotherm studies specified that ion exchange might play a prominent role.

Determination of synthetic ferric chelates used as fertilizers by liquid chromatography-electrospray/mass spectrometry in agricultural matrices.

PubMed

Alvarez-Fernández, Ana; Orera, Irene; Abadía, Javier; Abadía, Anunciación

2007-01-01

A high-performance liquid chromatography-electrospray ionization/mass spectrometry (time of flight) method has been developed for the simultaneous determination of synthetic Fe(III)-chelates used as fertilizers. Analytes included the seven major Fe(III)-chelates used in agriculture, Fe(III)-EDTA, Fe(III)-DTPA, Fe(III)-HEDTA, Fe(III)-CDTA, Fe(III)-o,oEDDHA, Fe(III)-o,pEDDHA, and Fe(III)-EDDHMA, and the method was validated using isotope labeled (57)Fe(III)-chelates as internal standards. Calibration curves had R values in the range 0.9962-0.9997. Limits of detection and quantification were in the ranges 3-164 and 14-945 pmol, respectively. Analyte concentrations could be determined between the limits of quantification and 25 muM (racemic and meso Fe(III)-o,oEDDHA and Fe(III)-EDDHMA) or 50 muM (Fe(III)-EDTA, Fe(III)-HEDTA, Fe(III)-DTPA, Fe(III)-CDTA and Fe(III)-o,pEDDHA). The average intraday repeatability values were approximately 0.5 and 5% for retention time and peak area, respectively, whereas the interday repeatability values were approximately 0.7 and 8% for retention time and peak area, respectively. The method was validated using four different agricultural matrices, including nutrient solution, irrigation water, soil solution, and plant xylem exudates, spiked with Fe(III)-chelate standards and their stable isotope-labeled corresponding chelates. Analyte recoveries found were in the ranges 92-101% (nutrient solution), 89-102% (irrigation water), 82-100% (soil solution), and 70-111% (plant xylem exudates). Recoveries depended on the analyte, with Fe(III)-EDTA and Fe(III)-DTPA showing the lowest recoveries (average values of 87 and 88%, respectively, for all agricultural matrices used), whereas for other analytes recoveries were between 91 and 101%. The method was also used to determine the real concentrations of Fe(III)-chelates in commercial fertilizers. Furthermore, the method is also capable of resolving two more synthetic Fe(III)-chelates, Fe(III)-EDDHSA and Fe(III)-EDDCHA, whose exact quantification is not currently possible because of lack of commercial standards.

Reinforcing loose foundation stones in trait-based plant ecology.

PubMed

Shipley, Bill; De Bello, Francesco; Cornelissen, J Hans C; Laliberté, Etienne; Laughlin, Daniel C; Reich, Peter B

2016-04-01

The promise of "trait-based" plant ecology is one of generalized prediction across organizational and spatial scales, independent of taxonomy. This promise is a major reason for the increased popularity of this approach. Here, we argue that some important foundational assumptions of trait-based ecology have not received sufficient empirical evaluation. We identify three such assumptions and, where possible, suggest methods of improvement: (i) traits are functional to the degree that they determine individual fitness, (ii) intraspecific variation in functional traits can be largely ignored, and (iii) functional traits show general predictive relationships to measurable environmental gradients.

NHANES III equations enhance early detection and mortality prediction of bronchiolitis obliterans syndrome after hematopoietic SCT

PubMed Central

Williams, KM; Hnatiuk, O; Mitchell, SA; Baird, K; Gadalla, SM; Steinberg, SM; Shelhamer, J; Carpenter, A; Avila, D; Taylor, T; Grkovic, L; Pulanic, D; Comis, LE; Blacklock-Schuver, B; Gress, RE; Pavletic, SZ

2017-01-01

Bronchiolitis obliterans syndrome (BOS) is a serious complication of chronic GVHD (cGVHD) following HSCT (hematopoietic SCT). The clinical diagnosis of BOS is based on pulmonary function test (PFT) abnormalities including: FEV1<75% predicted and obstructive FEV1/VC ratio, calculated using reference equations. We sought to determine if the frequency of clinical diagnoses and severity of BOS would be altered by using the recommended NHANES III vs older equations (Morris/Goldman/Bates, MGB) in 166 cGVHD patients, median age 48 (range: 12–67). We found that NHANES III equations significantly increased the prevalence of BOS, with an additional 11% (18/166) meeting diagnostic criteria by revealing low FEV1 (<75%) (P<0.0001), and six additional patients by obstructive ratio (vs MBG). Collectively, this led to an increase of BOS incidence from 17 (29/166) to 29% (41/166). For patients with severe BOS, (FEV1<35%), NHANES III equations correctly predicted death 71.4% vs 50% using MGB. In conclusion, the use of NHANES III equations markedly increases the proportion of cases meeting diagnostic criteria for BOS and improves prediction of survival. PMID:24419526

Cognitive Profiles of Adults with Asperger's Disorder, High-Functioning Autism, and Pervasive Developmental Disorder Not Otherwise Specified Based on the WAIS-III

ERIC Educational Resources Information Center

Kanai, Chieko; Tani, Masayuki; Hashimoto, Ryuichiro; Yamada, Takashi; Ota, Haruhisa; Watanabe, Hiromi; Iwanami, Akira; Kato, Nobumasa

2012-01-01

Little is known about the cognitive profiles of high-functioning Pervasive Developmental Disorders (PDD) in adults based on the Wechsler Intelligence Scale III (WAIS-III). We examined cognitive profiles of adults with no intellectual disability (IQ greater than 70), and in adults with Asperger's disorder (AS; n = 47), high-functioning autism (HFA;…

Relationship between communication skills and gross motor function in preschool-aged children with cerebral palsy.

PubMed

Coleman, Andrea; Weir, Kelly A; Ware, Robert S; Boyd, Roslyn N

2013-11-01

To explore the communication skills of children with cerebral palsy (CP) at 24 months' corrected age with reference to typically developing children, and to determine the relationship between communication ability, gross motor function, and other comorbidities associated with CP. Prospective, cross-sectional, population-based cohort study. General community. Children with CP (N=124; mean age, 24mo; functional severity on Gross Motor Function Classification System [GMFCS]: I=47, II=14, III=22, IV=19, V=22). Not applicable. Parents reported communication skills on the Communication and Symbolic Behavior Scales Developmental Profile (CSBS-DP) Infant-Toddler Checklist. Two independent physiotherapists classified motor type, distribution, and GMFCS. Data on comorbidities were obtained from parent interviews and medical records. Children with mild CP (GMFCS I/II) had mean CSBS-DP scores that were 0.5 to 0.6 SD below the mean for typically developing peers, while those with moderate-severe impairment (GMFCS III-V) were 1.4 to 2.6 SD below the mean. GMFCS was significantly associated with performance on the CSBS-DP (F=18.55, P<.001), with gross motor ability accounting for 38% of the variation in communication. Poorer communication was strongly associated with gross motor function and full-term birth. Preschool-aged children with CP, with more severe gross motor impairment, showed delayed communication, while children with mild motor impairment were less vulnerable. Term-born children had significantly poorer communication than those born prematurely. Because a portion of each gross motor functional severity level is at risk, this study reinforces the need for early monitoring of communication development for all children with CP. Copyright © 2013 American Congress of Rehabilitation Medicine. Published by Elsevier Inc. All rights reserved.

LDL-oxidation, serum uric acid, kidney function and pulse-wave velocity: Data from the Brisighella Heart Study cohort.

PubMed

Cicero, Arrigo F G; Kuwabara, Masanari; Johnson, Richard; Bove, Marilisa; Fogacci, Federica; Rosticci, Martina; Giovannini, Marina; D'Addato, Sergio; Borghi, Claudio

2018-06-15

Serum uric acid (SUA) and oxidized LDL (oxLDL) may be associated with arterial aging. The aim of our study was to evaluate the relationship between SUA, oxLDL and arterial stiffness in subjects with normal renal function and in patients with mild or moderate renal impairment. From the database of the 2012 Brisighella Heart Study, we compared age-matched adult, non-smoker subjects without cardiovascular disease and with normal renal function (n = 205), subjects with stage II chronic kidney disease (CKD) (n = 118) and subjects with stage III CKD (n = 94). All subjects underwent a determination of the LDL oxidative susceptibility, oxLDL levels, SUA and Pulse Wave Velocity (PWV). By univariate analysis, PWV correlated with a large number of clinical, haemodynamic and metabolic parameters, including estimated glomerular filtration rate (eGFR) in subjects with normal renal function and in those with stage II or III CKD. Stepwise multiple regression analyses showed that in the presence of normal renal function or stage II CKD, the main predictors of PWV were age, systolic blood pressure (SBP), ox-LDL, apolipoprotein B and SUA (p < 0.05), while in the presence of stage III CKD only age, SBP and apolipoprotein B remained significant (p < 0.05). Both ox-LDL and SUA independently predicts PWV only in subjects with normal or mildly reduced renal function, but not in the subjects with more compromised eGFR. This study confirms the complex relationship of SUA with cardiovascular and metabolic disease in the patient with established renal disease. Copyright © 2018 Elsevier B.V. All rights reserved.

Spectrophotometric Determination of Chromium (III) with the Disodium Salt of (Ethylenediamine) tetraacetic Acid (Complexon III); DETERMINACION ESPECTROFOTOMETRICA DE CROMO (III) CON LA SAL DISODICA DEL ACIDO ETILEN-DIAMINO-TETRA-ACETICO (COMPLEXONA III)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cellini, R.F.; Valiente, E.A.

1956-01-01

A spectrophotometric method for Cr (III) determination is established: hot and weak acid solutions are treated by disodium (ethylenediamine)tetraacetic acid (complexoneIII) yielding a very stable violet chelate, which follows Beer's law between 1 and 7 gamma Cr(III)/ml. These concentrations are employed in the experiences of this work. The absorption spectrum of Cr(III)-complexone-III has two maximums at 396 and 538 m mu . The maximum at 538 mu m is utilized in this method. Time, temperature, pH, and complexone-III concentration are studied and the best experimental conditions are fixed. (auth)

CIITA promoter I CARD-deficient mice express functional MHC class II genes in myeloid and lymphoid compartments.

PubMed

Zinzow-Kramer, W M; Long, A B; Youngblood, B A; Rosenthal, K M; Butler, R; Mohammed, A-U-R; Skountzou, I; Ahmed, R; Evavold, B D; Boss, J M

2012-06-01

Three distinct promoters control the master regulator of major histocompatibility complex (MHC) class II expression, class II transactivator (CIITA), in a cell type-specific manner. Promoter I (pI) CIITA, expressed primarily by dendritic cells (DCs) and macrophages, expresses a unique isoform that contains a caspase-recruitment domain (CARD). The activity and function of this isoform are not understood, but are believed to enhance the function of CIITA in antigen-presenting cells. To determine whether isoform I of CIITA has specific functions, CIITA mutant mice were created in which isoform I was replaced with isoform III sequences. Mice in which pI and the CARD-encoding exon were deleted were also created. No defect in the formation of CD4 T cells, the ability to respond to a model antigen or bacterial or viral challenge was observed in mice lacking CIITA isoform I. Although CIITA and MHC-II expression was decreased in splenic DCs, pI knockout animals expressed CIITA from downstream promoters, suggesting that control of pI activity is mediated by unknown distal elements that could act at pIII, the B-cell promoter. Thus, no critical function is linked to the CARD domain of CIITA isoform I with respect to basic immune system development, function and challenge.

Methods for determining soluble and insoluble Cr III and Cr VI compounds in welding fumes.

PubMed

Matczak, W; Chmielnicka, J

1989-01-01

An analytical procedure for simultaneous determination of soluble and insoluble Cr III and Cr VI compounds in welding fumes has been proposed. In the welding fume samples collected on a membrane filter, total chromium was determined with atomic absorption spectrophotometry (AAS). Glass filters with collected samples were divided into two parts. In one part of the sample, soluble and insoluble chromium was determined by means of AAS. The separation of soluble chromium III and VI was carried out on diphenylcarbazide resin. In the second part of the sample total chromium VI was determined by means of the colorimetric method with s-diphenylcarbazide. The difference in the results of these determinations allowed the calculation of the content of total Cr III, Cr III insolub. and Cr VI insolub. The results of determining chromium compounds in welding fumes samples collected in the welder's breathing zone and in experimental chambers are also presented in this paper. The content of total chromium in the fumes determined by AAS (from a membrane filtr) and that calculated from the sum of soluble and insoluble chromium (from a glass filter) were concordant and within the limits of the admissible error for the method. Total chromium content in welding fume samples collected individually was found to range from 2.4-4.2%. The percentage of particular chromium compounds as compared to total chromium (100%) amounted: total Cr III--34%, total Cr VI--66%, soluble chromium--66% and in this Cr III--20% and Cr VI--43%, insoluble chromium--34% and in this: Cr III--14% and Cr VI--20%.

The regulon of the RNA chaperone CspA and its auto-regulation in Staphylococcus aureus.

PubMed

Caballero, Carlos J; Menendez-Gil, Pilar; Catalan-Moreno, Arancha; Vergara-Irigaray, Marta; García, Begoña; Segura, Víctor; Irurzun, Naiara; Villanueva, Maite; Ruiz de Los Mozos, Igor; Solano, Cristina; Lasa, Iñigo; Toledo-Arana, Alejandro

2018-02-16

RNA-binding proteins (RBPs) are essential to fine-tune gene expression. RBPs containing the cold-shock domain are RNA chaperones that have been extensively studied. However, the RNA targets and specific functions for many of them remain elusive. Here, combining comparative proteomics and RBP-immunoprecipitation-microarray profiling, we have determined the regulon of the RNA chaperone CspA of Staphylococcus aureus. Functional analysis revealed that proteins involved in carbohydrate and ribonucleotide metabolism, stress response and virulence gene expression were affected by cspA deletion. Stress-associated phenotypes such as increased bacterial aggregation and diminished resistance to oxidative-stress stood out. Integration of the proteome and targetome showed that CspA post-transcriptionally modulates both positively and negatively the expression of its targets, denoting additional functions to the previously proposed translation enhancement. One of these repressed targets was its own mRNA, indicating the presence of a negative post-transcriptional feedback loop. CspA bound the 5'UTR of its own mRNA disrupting a hairpin, which was previously described as an RNase III target. Thus, deletion of the cspA 5'UTR abrogated mRNA processing and auto-regulation. We propose that CspA interacts through a U-rich motif, which is located at the RNase III cleavage site, portraying CspA as a putative RNase III-antagonist.

49 CFR 232.211 - Class III brake tests-trainline continuity inspection.

Code of Federal Regulations, 2012 CFR

2012-10-01

... pressure is being restored, the operator of the train shall know that the air brakes function as intended... determined that the brakes on the rear car of the train apply and release in response to air pressure changes... train that has previously received a Class I brake test and that has not been off air for more than four...

49 CFR 232.211 - Class III brake tests-trainline continuity inspection.

Code of Federal Regulations, 2011 CFR

2011-10-01

... pressure is being restored, the operator of the train shall know that the air brakes function as intended... determined that the brakes on the rear car of the train apply and release in response to air pressure changes... train that has previously received a Class I brake test and that has not been off air for more than four...

49 CFR 232.211 - Class III brake tests-trainline continuity inspection.

Code of Federal Regulations, 2010 CFR

2010-10-01

... pressure is being restored, the operator of the train shall know that the air brakes function as intended... determined that the brakes on the rear car of the train apply and release in response to air pressure changes... train that has previously received a Class I brake test and that has not been off air for more than four...

49 CFR 232.211 - Class III brake tests-trainline continuity inspection.

Code of Federal Regulations, 2013 CFR

2013-10-01

... pressure is being restored, the operator of the train shall know that the air brakes function as intended... determined that the brakes on the rear car of the train apply and release in response to air pressure changes... train that has previously received a Class I brake test and that has not been off air for more than four...

49 CFR 232.211 - Class III brake tests-trainline continuity inspection.

Code of Federal Regulations, 2014 CFR

2014-10-01

... pressure is being restored, the operator of the train shall know that the air brakes function as intended... determined that the brakes on the rear car of the train apply and release in response to air pressure changes... train that has previously received a Class I brake test and that has not been off air for more than four...

Biosorptive removal of inorganic arsenic species and fluoride from aqueous medium by the stem of Tecomella undulate.

PubMed

Brahman, Kapil Dev; Kazi, Tasneem Gul; Baig, Jameel Ahmed; Afridi, Hassan Imran; Arain, Sadaf Sadia; Saraj, Saima; Arain, Muhammad B; Arain, Salma Aslam

2016-05-01

Simultaneous removal of fluoride (F(-)), inorganic arsenic species, As(III) and As(V), from aqueous samples has been performed using an economic indigenous biosorbent (Stem of Tecomella undulata). The inorganic As species in water samples before and after biosorption were determined by cloud point and solid phase extraction methods, while F(-) was determined by ion chromatography. Batch experiments were carried out to evaluate the equilibrium adsorption isotherm studies for As(III), As(V) and F(-) in aqueous solutions. Several parameters of biosorption were optimized such as pH, biomass dosage, analytes concentration, time and temperature. The surface of biosorbent was characterized by SEM and FTIR. The FTIR study indicated the presence of carbonyl and amine functional groups which may have important role in the sorption/removal of these ions. Thermodynamic and kinetic study indicated that the biosorption of As(III), As(V) and F(-) were spontaneous, exothermic and followed by pseudo-second-order. Meanwhile, the interference study revealed that there was no significant effect of co-existing ions for the removal of inorganic As species and F(-) from aqueous samples (p > 0.05). It was observed that the indigenous biosorbent material simultaneously adsorbed As(III) (108 μg g(-1)), As(V) (159 μg g(-1)) and F(-) (6.16 mg g(-1)) from water at optimized conditions. The proposed biosorbent was effectively regenerated and efficiently used for several experiments, to remove the As(III), As(V) and F(-) from real water sample collected from endemic area of Pakistan. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ion temperature measurements of indirect-drive implosions with the neutron time-of-flight detector on SG-III laser facility

NASA Astrophysics Data System (ADS)

Chen, Zhongjing; Zhang, Xing; Pu, Yudong; Yan, Ji; Huang, Tianxuan; Jiang, Wei; Yu, Bo; Chen, Bolun; Tang, Qi; Song, Zifeng; Chen, Jiabin; Zhan, Xiayu; Liu, Zhongjie; Xie, Xufei; Jiang, Shaoen; Liu, Shenye

2018-02-01

The accuracy of the determination of the burn-averaged ion temperature of inertial confinement fusion implosions depends on the unfold process, including deconvolution and convolution methods, and the function, i.e., the detector response, used to fit the signals measured by neutron time-of-flight (nToF) detectors. The function given by Murphy et al. [Rev. Sci. Instrum. 68(1), 610-613 (1997)] has been widely used in Nova, Omega, and NIF. There are two components, i.e., fast and slow, and the contribution of scattered neutrons has not been dedicatedly considered. In this work, a new function, based on Murphy's function has been employed to unfold nToF signals. The contribution of scattered neutrons is easily included by the convolution of a Gaussian response function and an exponential decay. The ion temperature is measured by nToF with the new function. Good agreement with the ion temperature determined by the deconvolution method has been achieved.

Upper functional gastrointestinal disorders in young adults.

PubMed

Adibi, Peyman; Behzad, Ebrahim; Shafieeyan, Mohammad; Toghiani, Ali

2012-01-01

Functional Gastrointestinal disorders (FGID) are common disorders in gastroenterology which are common in young adults. The aim of this study is evaluating the prevalence of upper FGID in iranian young adults. This was a cross-sectional study which was on 995 persons who were going to marry. A ROME III based questionnaire was used to determine the frequency of upper GI Syndromes among the sample population. Our results determined 74 subjects had functional dyspepsia (36 subjects diagnosed as postprandial distress syndrome patient and Epigastric pain syndrome was seen in 38 subjects). Functional heartburn was diagnosed in 52 participants. Globus was seen in 35 subjects and 41 had unspecified excessive belching. Many epidemiologic studies were done all around the world but there are different reports about prevalence and incidence of FGIDs. Our results were agreed with reported prevalence of FGIDs in Iran in adults. And our findings were agreed with some other Asian studies.

Stability of the DSM-5 Section III pathological personality traits and their longitudinal associations with psychosocial functioning in personality disordered individuals.

PubMed

Wright, Aidan G C; Calabrese, William R; Rudick, Monica M; Yam, Wern How; Zelazny, Kerry; Williams, Trevor F; Rotterman, Jane H; Simms, Leonard J

2015-02-01

This study was conducted to establish (a) the stability of the DSM-5 Section III personality disorder (PD) traits, (b) whether these traits predict future psychosocial functioning, and (c) whether changes in traits track with changes in psychosocial functioning across time. Ninety-three outpatients (61% female) diagnosed with at least 1 PD completed patient-report measures at 2 time-points (M time between assessments = 1.44 years), including the Personality Inventory for the DSM-5 and several measures of psychosocial functioning. Effect sizes of rank-order and mean-level change were calculated. In addition, Time 1 traits were used to predict functioning measures at Time 2. Finally, latent change score models were estimated for DSM-5 Section III traits and functioning measures, and correlations among latent change scores were calculated to establish the relationship between change in traits and functional outcomes. Findings demonstrated that the DSM-5 Section III traits were highly stable in terms of normative (i.e., mean-level) change and rank-order stability over the course of the study. Furthermore, traits prospectively predicted psychosocial functioning. However, at the individual level traits and functioning were not entirely static over the study, and change in individuals' functioning tracked with changes in trait levels. These findings demonstrate that the DSM-5 Section III traits are highly stable consistent with the definition of PD, prospectively predictive of psychosocial functioning, and are dynamically associated with functioning over time. This study provides important evidence in support of the DSM-5 Section III PD model. (PsycINFO Database Record (c) 2015 APA, all rights reserved).

Surface Complexation Modeling of Eu(III) and U(VI) Interactions with Graphene Oxide.

PubMed

Xie, Yu; Helvenston, Edward M; Shuller-Nickles, Lindsay C; Powell, Brian A

2016-02-16

Graphene oxide (GO) has great potential for actinide removal due to its extremely high sorption capacity, but the mechanism of sorption remains unclear. In this study, the carboxylic functional group and an unexpected sulfonate functional group on GO were characterized as the reactive surface sites and quantified via diffuse layer modeling of the GO acid/base titrations. The presence of sulfonate functional group on GO was confirmed using elemental analysis and X-ray photoelectron spectroscopy. Batch experiments of Eu(III) and U(VI) sorption to GO as the function of pH (1-8) and as the function of analyte concentration (10-100, 000 ppb) at a constant pH ≈ 5 were conducted; the batch sorption results were modeled simultaneously using surface complexation modeling (SCM). The SCM indicated that Eu(III) and U(VI) complexation to carboxylate functional group is the main mechanism for their sorption to GO; their complexation to the sulfonate site occurred at the lower pH range and the complexation of Eu(III) to sulfonate site are more significant than that of U(VI). Eu(III) and U(VI) facilitated GO aggregation was observed with high Eu(III) and U(VI) concentration and may be caused by surface charge neutralization of GO after sorption.

Natural history of echocardiographic abnormalities in mucopolysaccharidosis III.

PubMed

Wilhelm, Carolyn M; Truxal, Kristen V; McBride, Kim L; Kovalchin, John P; Flanigan, Kevin M

2018-06-01

Mucopolysaccharidosis (MPS) type III, Sanfilippo Syndrome, is an autosomal recessive lysosomal storage disorder. MPS I and II patients often develop cardiac involvement leading to early mortality, however there are limited data in MPS III. The objective of this study is to describe cardiac abnormalities in a large group of MPS III patients followed in a longitudinal natural history study designed to determine outcome measures for gene transfer trials. A single center study of MPS III patients who were enrolled in the Nationwide Children's Hospital natural history study in 2014. Two cardiologists reviewed all patient echocardiograms for anatomic, valvular, and functional abnormalities. Valve abnormalities were defined as abnormal morphology, trivial mitral regurgitation (MR) with abnormal morphology or at least mild MR, and any aortic regurgitation (AR). Abnormal left ventricular (LV) function was defined as ejection fraction < 50%. Group comparisons were assessed using two-sample t-tests or Wilcoxon rank sum tests for continuous variables and chi-square or Fisher's exact tests for categorical variables. Twenty-five patients, 15 Type A and 10 Type B MPS III, underwent 45 echocardiograms. Fifteen patients (60%) demonstrated an abnormal echocardiographic finding with age at first abnormal echocardiogram within the study being 6.8 ± 2.8 years. Left-sided valve abnormalities were common over time: 7 mitral valve thickening, 2 mitral valve prolapse, 16 MR (8 mild, 8 trivial), 3 aortic valve thickening, and 9 AR (7 mild, 2 trivial). Two patients had asymmetric LV septal hypertrophy. No valvular stenosis or ventricular function abnormalities were noted. Incidental findings included: mild aortic root dilation (2), bicommissural aortic valve (1), and mild tricuspid regurgitation (3). Individuals with Sanfilippo A and B demonstrate a natural history of cardiac involvement with valvular abnormalities most common. In short-term follow up, patients demonstrated only mild progression of abnormalities, none requiring intervention. Valvular disease prevalence is similar to MPS I and II, but appears less severe. These findings raise no specific concerns for gene transfer trials in patients in this age range. Copyright © 2018 Elsevier Inc. All rights reserved.

An MBE growth facility for real-time in situ synchrotron x-ray topography studies of strained-layer III-V epitaxial materials

NASA Astrophysics Data System (ADS)

Whitehouse, C. R.; Barnett, S. J.; Soley, D. E. J.; Quarrell, J.; Aldridge, S. J.; Cullis, A. G.; Emeny, M. T.; Johnson, A. D.; Clarke, G. F.; Lamb, W.; Tanner, B. K.; Cottrell, S.; Lunn, B.; Hogg, C.; Hagston, W.

1992-01-01

This paper describes a unique combined UHV MBE growth x-ray topography facility designed to allow the first real-time synchrotron radiation x-ray topography study of strained-layer III-V growth processes. This system will enable unambiguous determination of dislocation nucleation and multiplication processes as a function of controlled variations in growth conditions, and also during post-growth thermal processing. The planned experiments have placed very stringent demands upon the engineering design of the system, and design details regarding the growth chamber; sample manipulator, x-ray optics, and real-time imaging systems are described. Results obtained during a feasibility study are also presented.

An MBE growth facility for real-time in situ synchrotron x-ray topography studies of strained-layer III--V epitaxial materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Whitehouse, C.R.; Barnett, S.J.; Soley, D.E.J.

1992-01-01

This paper describes a unique combined UHV MBE growth x-ray topography facility designed to allow the first real-time synchrotron radiation x-ray topography study of strained-layer III--V growth processes. This system will enable unambiguous determination of dislocation nucleation and multiplication processes as a function of controlled variations in growth conditions, and also during post-growth thermal processing. The planned experiments have placed very stringent demands upon the engineering design of the system, and design details regarding the growth chamber; sample manipulator, x-ray optics, and real-time imaging systems are described. Results obtained during a feasibility study are also presented.

Hyperglycemia-conditioned increase in alpha-2-macroglobulin in healthy normal subjects: a phenomenon correlated with deficient antithrombin III activity.

PubMed

Ceriello, A; Quatraro, A; Dello Russo, P; Marchi, E; Barbanti, M; Giugliano, D

1989-01-01

Induced hyperglycemia in normal subjects increases alpha 2-macroglobulin (alpha 2M) activity and alpha 2M concentration and reduces antithrombin III (ATIII) activity, while it does not affect ATIII plasma concentration. Hyperglycemia-determined variations in ATIII activity and alpha 2M molecules are correlated in an inverse and parallel fashion. A compensatory role for the increase in alpha 2M in the regulation of the coagulation system may be hypothesized. Moreover, these data provide evidence that hyperglycemia may decrease, directly, the biological function of some proteins and may influence the levels of some risk factors for the development of complications in diabetes.

COMBREX-DB: an experiment centered database of protein function: knowledge, predictions and knowledge gaps.

PubMed

Chang, Yi-Chien; Hu, Zhenjun; Rachlin, John; Anton, Brian P; Kasif, Simon; Roberts, Richard J; Steffen, Martin

2016-01-04

The COMBREX database (COMBREX-DB; combrex.bu.edu) is an online repository of information related to (i) experimentally determined protein function, (ii) predicted protein function, (iii) relationships among proteins of unknown function and various types of experimental data, including molecular function, protein structure, and associated phenotypes. The database was created as part of the novel COMBREX (COMputational BRidges to EXperiments) effort aimed at accelerating the rate of gene function validation. It currently holds information on ∼ 3.3 million known and predicted proteins from over 1000 completely sequenced bacterial and archaeal genomes. The database also contains a prototype recommendation system for helping users identify those proteins whose experimental determination of function would be most informative for predicting function for other proteins within protein families. The emphasis on documenting experimental evidence for function predictions, and the prioritization of uncharacterized proteins for experimental testing distinguish COMBREX from other publicly available microbial genomics resources. This article describes updates to COMBREX-DB since an initial description in the 2011 NAR Database Issue. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

Functional Incompatibility between the Generic NF-κB Motif and a Subtype-Specific Sp1III Element Drives the Formation of the HIV-1 Subtype C Viral Promoter

PubMed Central

Verma, Anjali; Rajagopalan, Pavithra; Lotke, Rishikesh; Varghese, Rebu; Selvam, Deepak; Kundu, Tapas K.

2016-01-01

ABSTRACT Of the various genetic subtypes of human immunodeficiency virus types 1 and 2 (HIV-1 and HIV-2) and simian immunodeficiency virus (SIV), only in subtype C of HIV-1 is a genetically variant NF-κB binding site found at the core of the viral promoter in association with a subtype-specific Sp1III motif. How the subtype-associated variations in the core transcription factor binding sites (TFBS) influence gene expression from the viral promoter has not been examined previously. Using panels of infectious viral molecular clones, we demonstrate that subtype-specific NF-κB and Sp1III motifs have evolved for optimal gene expression, and neither of the motifs can be replaced by a corresponding TFBS variant. The variant NF-κB motif binds NF-κB with an affinity 2-fold higher than that of the generic NF-κB site. Importantly, in the context of an infectious virus, the subtype-specific Sp1III motif demonstrates a profound loss of function in association with the generic NF-κB motif. An additional substitution of the Sp1III motif fully restores viral replication, suggesting that the subtype C-specific Sp1III has evolved to function with the variant, but not generic, NF-κB motif. A change of only two base pairs in the central NF-κB motif completely suppresses viral transcription from the provirus and converts the promoter into heterochromatin refractory to tumor necrosis factor alpha (TNF-α) induction. The present work represents the first demonstration of functional incompatibility between an otherwise functional NF-κB motif and a unique Sp1 site in the context of an HIV-1 promoter. Our work provides important leads as to the evolution of the HIV-1 subtype C viral promoter with relevance for gene expression regulation and viral latency. IMPORTANCE Subtype-specific genetic variations provide a powerful tool to examine how these variations offer a replication advantage to specific viral subtypes, if any. Only in subtype C of HIV-1 are two genetically distinct transcription factor binding sites positioned at the most critical location of the viral promoter. Since a single promoter regulates viral gene expression, the promoter variations can play a critical role in determining the replication fitness of the viral strains. Our work for the first time provides a scientific explanation for the presence of a unique NF-κB binding motif in subtype C, a major HIV-1 genetic family responsible for half of the global HIV-1 infections. The results offer compelling evidence that the subtype C viral promoter not only is stronger but also is endowed with a qualitative gain-of-function advantage. The genetically variant NF-κB and the Sp1III motifs may be respond differently to specific cell signal pathways, and these mechanisms must be examined. PMID:27194770

Method of trivalent chromium concentration determination by atomic spectrometry

DOEpatents

Reheulishvili, Aleksandre N [Tbilisi, 0183, GE; Tsibakhashvili, Neli Ya [Tbilisi, 0101, GE

2006-12-12

A method is disclosed for determining the concentration of trivalent chromium Cr(III) in a sample. The addition of perchloric acid has been found to increase the atomic chromium spectrometric signal due to Cr(III), while leaving the signal due to hexavalent chromium Cr(VI) unchanged. This enables determination of the Cr(III) concentration without pre-concentration or pre-separation from chromium of other valences. The Cr(III) concentration may be measured using atomic absorption spectrometry, atomic emission spectrometry or atomic fluorescence spectrometry.

Highly sensitive catalytic spectrophotometric determination of ruthenium

NASA Astrophysics Data System (ADS)

Naik, Radhey M.; Srivastava, Abhishek; Prasad, Surendra

2008-01-01

A new and highly sensitive catalytic kinetic method (CKM) for the determination of ruthenium(III) has been established based on its catalytic effect on the oxidation of L-phenylalanine ( L-Pheala) by KMnO 4 in highly alkaline medium. The reaction has been followed spectrophotometrically by measuring the decrease in the absorbance at 526 nm. The proposed CKM is based on the fixed time procedure under optimum reaction conditions. It relies on the linear relationship where the change in the absorbance (Δ At) versus added Ru(III) amounts in the range of 0.101-2.526 ng ml -1 is plotted. Under the optimum conditions, the sensitivity of the proposed method, i.e. the limit of detection corresponding to 5 min is 0.08 ng ml -1, and decreases with increased time of analysis. The method is featured with good accuracy and reproducibility for ruthenium(III) determination. The ruthenium(III) has also been determined in presence of several interfering and non-interfering cations, anions and polyaminocarboxylates. No foreign ions interfered in the determination ruthenium(III) up to 20-fold higher concentration of foreign ions. In addition to standard solutions analysis, this method was successfully applied for the quantitative determination of ruthenium(III) in drinking water samples. The method is highly sensitive, selective and very stable. A review of recently published catalytic spectrophotometric methods for the determination of ruthenium(III) has also been presented for comparison.

Efficient Energy Transfer from Near-Infrared Emitting Gold Nanoparticles to Pendant Ytterbium(III).

PubMed

Crawford, Scott E; Andolina, Christopher M; Kaseman, Derrick C; Ryoo, Bo Hyung; Smith, Ashley M; Johnston, Kathryn A; Millstone, Jill E

2017-12-13

Here, we demonstrate efficient energy transfer from near-infrared-emitting ortho-mercaptobenzoic acid-capped gold nanoparticles (AuNPs) to pendant ytterbium(III) cations. These functional materials combine the high molar absorptivity (1.21 × 10 6 M -1 cm -1 ) and broad excitation features (throughout the UV and visible regions) of AuNPs with the narrow emissive properties of lanthanides. Interaction between the AuNP ligand shell and ytterbium is determined using both nuclear magnetic resonance and electron microscopy measurements. In order to identify the mechanism of this energy transfer process, the distance of the ytterbium(III) from the surface of the AuNPs is systematically modulated by changing the size of the ligand appended to the AuNP. By studying the energy transfer efficiency from the various AuNP conjugates to pendant ytterbium(III) cations, a Dexter-type energy transfer mechanism is suggested, which is an important consideration for applications ranging from catalysis to energy harvesting. Taken together, these experiments lay a foundation for the incorporation of emissive AuNPs in energy transfer systems.

βIII Spectrin Is Necessary for Formation of the Constricted Neck of Dendritic Spines and Regulation of Synaptic Activity in Neurons.

PubMed

Efimova, Nadia; Korobova, Farida; Stankewich, Michael C; Moberly, Andrew H; Stolz, Donna B; Wang, Junling; Kashina, Anna; Ma, Minghong; Svitkina, Tatyana

2017-07-05

Dendritic spines are postsynaptic structures in neurons often having a mushroom-like shape. Physiological significance and cytoskeletal mechanisms that maintain this shape are poorly understood. The spectrin-based membrane skeleton maintains the biconcave shape of erythrocytes, but whether spectrins also determine the shape of nonerythroid cells is less clear. We show that βIII spectrin in hippocampal and cortical neurons from rodent embryos of both sexes is distributed throughout the somatodendritic compartment but is particularly enriched in the neck and base of dendritic spines and largely absent from spine heads. Electron microscopy revealed that βIII spectrin forms a detergent-resistant cytoskeletal network at these sites. Knockdown of βIII spectrin results in a significant decrease in the density of dendritic spines. Surprisingly, the density of presynaptic terminals is not affected by βIII spectrin knockdown. However, instead of making normal spiny synapses, the presynaptic structures in βIII spectrin-depleted neurons make shaft synapses that exhibit increased amplitudes of miniature EPSCs indicative of excessive postsynaptic excitation. Thus, βIII spectrin is necessary for formation of the constricted shape of the spine neck, which in turn controls communication between the synapse and the parent dendrite to prevent excessive excitation. Notably, mutations of SPTNB2 encoding βIII spectrin are associated with neurodegenerative syndromes, spinocerebellar ataxia Type 5, and spectrin-associated autosomal recessive cerebellar ataxia Type 1, but molecular mechanisms linking βIII spectrin functions to neuronal pathologies remain unresolved. Our data suggest that spinocerebellar ataxia Type 5 and spectrin-associated autosomal recessive cerebellar ataxia Type 1 pathology likely arises from poorly controlled synaptic activity that leads to excitotoxicity and neurodegeneration. SIGNIFICANCE STATEMENT Dendritic spines are small protrusions from neuronal dendrites that make synapses with axons of other neurons in the brain. Dendritic spines usually have a mushroom-like shape, which is essential for brain functions, because aberrant spine morphology is associated with many neuropsychiatric disorders. The bulbous head of a mushroom-shaped spine makes the synapse, whereas the narrow neck transmits the incoming signals to the dendrite and supposedly controls the signal propagation. We show that a cytoskeletal protein βIII spectrin plays a key role for the formation of narrow spine necks. In the absence of βIII spectrin, dendritic spines collapse onto dendrites. As a result, synaptic strength exceeds acceptable levels and damages neurons, explaining pathology of human syndromes caused by βIII spectrin mutations. Copyright © 2017 the authors 0270-6474/17/376443-18$15.00/0.

βIII Spectrin Is Necessary for Formation of the Constricted Neck of Dendritic Spines and Regulation of Synaptic Activity in Neurons

PubMed Central

Efimova, Nadia; Korobova, Farida; Moberly, Andrew H.; Stolz, Donna B.; Wang, Junling; Kashina, Anna; Ma, Minghong

2017-01-01

Dendritic spines are postsynaptic structures in neurons often having a mushroom-like shape. Physiological significance and cytoskeletal mechanisms that maintain this shape are poorly understood. The spectrin-based membrane skeleton maintains the biconcave shape of erythrocytes, but whether spectrins also determine the shape of nonerythroid cells is less clear. We show that βIII spectrin in hippocampal and cortical neurons from rodent embryos of both sexes is distributed throughout the somatodendritic compartment but is particularly enriched in the neck and base of dendritic spines and largely absent from spine heads. Electron microscopy revealed that βIII spectrin forms a detergent-resistant cytoskeletal network at these sites. Knockdown of βIII spectrin results in a significant decrease in the density of dendritic spines. Surprisingly, the density of presynaptic terminals is not affected by βIII spectrin knockdown. However, instead of making normal spiny synapses, the presynaptic structures in βIII spectrin-depleted neurons make shaft synapses that exhibit increased amplitudes of miniature EPSCs indicative of excessive postsynaptic excitation. Thus, βIII spectrin is necessary for formation of the constricted shape of the spine neck, which in turn controls communication between the synapse and the parent dendrite to prevent excessive excitation. Notably, mutations of SPTNB2 encoding βIII spectrin are associated with neurodegenerative syndromes, spinocerebellar ataxia Type 5, and spectrin-associated autosomal recessive cerebellar ataxia Type 1, but molecular mechanisms linking βIII spectrin functions to neuronal pathologies remain unresolved. Our data suggest that spinocerebellar ataxia Type 5 and spectrin-associated autosomal recessive cerebellar ataxia Type 1 pathology likely arises from poorly controlled synaptic activity that leads to excitotoxicity and neurodegeneration. SIGNIFICANCE STATEMENT Dendritic spines are small protrusions from neuronal dendrites that make synapses with axons of other neurons in the brain. Dendritic spines usually have a mushroom-like shape, which is essential for brain functions, because aberrant spine morphology is associated with many neuropsychiatric disorders. The bulbous head of a mushroom-shaped spine makes the synapse, whereas the narrow neck transmits the incoming signals to the dendrite and supposedly controls the signal propagation. We show that a cytoskeletal protein βIII spectrin plays a key role for the formation of narrow spine necks. In the absence of βIII spectrin, dendritic spines collapse onto dendrites. As a result, synaptic strength exceeds acceptable levels and damages neurons, explaining pathology of human syndromes caused by βIII spectrin mutations. PMID:28576936

DOE Office of Scientific and Technical Information (OSTI.GOV)

Diaz, A.; Valdez, V; Rudino-Pinera, E

Neurospora crassa has two large-subunit catalases, CAT-1 and CAT-3. CAT-1 is associated with non-growing cells and accumulates particularly in asexual spores; CAT-3 is associated with growing cells and is induced under different stress conditions. It is our interest to elucidate the structure-function relationships in large-subunit catalases. Here we have determined the CAT-3 crystal structure and compared it with the previously determined CAT-1 structure. Similar to CAT-1, CAT-3 hydrogen peroxide (H{sub 2}O{sub 2}) saturation kinetics exhibited two components, consistent with the existence of two active sites: one saturated in the millimolar range and the other in the molar range. In themore » CAT-1 structure, we found three interesting features related to its unusual kinetics: (a) a constriction in the channel that conveys H{sub 2}O{sub 2} to the active site; (b) a covalent bond between the tyrosine, which forms the fifth coordination bound to the iron of the heme, and a vicinal cysteine; (c) oxidation of the pyrrole ring III to form a cis-hydroxyl group in C5 and a cis-{gamma}-spirolactone in C6. The site of heme oxidation marks the starts of the central channel that communicates to the central cavity and the shortest way products can exit the active site. CAT-3 has a similar constriction in its major channel, which could function as a gating system regulated by the H{sub 2}O{sub 2} concentration before the gate. CAT-3 functional tyrosine is not covalently bonded, but has instead the electron relay mechanism described for the human catalase to divert electrons from it. Pyrrole ring III in CAT-3 is not oxidized as it is in other large-subunit catalases whose structure has been determined. Different in CAT-3 from these enzymes is an occupied central cavity. Results presented here indicate that CAT-3 and CAT-1 enzymes represent a functional group of catalases with distinctive structural characteristics that determine similar kinetics.« less

Exposure to As(III) and As(V) changes the Ca²⁺-activation properties of the two major fibre types from the chelae of the freshwater crustacean Cherax destructor.

PubMed

Williams, Gemma; Snow, Elizabeth T; West, Jan M

2014-10-01

Arsenic is a known carcinogen found in the soil in gold mining regions at concentrations thousands of times greater than gold. Mining releases arsenic into the environment and surrounding water bodies. The main chemical forms of arsenic found in the environment are inorganic arsenite (As(III)) and arsenate (As(V)). Yabbies (Cherax destructor) accumulate arsenic at levels comparable to those in the sediment of their environment but the effect on their physiological function is not known. The effects of arsenic exposure (10 ppm sodium arsenite, AsNaO2 - 5.7 ppm As(III)) and 10 ppm arsenic acid, Na2HAsO4·7H2O - 2.6 ppm As(V)) for 40 days on the contractile function of the two major fibre types from the chelae were determined. After exposure, individual fibres were isolated from the chela, "skinned" (membrane removed) and attached to the force recording apparatus. Contraction was induced in solutions containing increasing [Ca(2+)] until a maximum Ca(2+)-activation was obtained. Submaximal force responses were plotted as a percentage of the maximum Ca(2+)-activated force. As(V) exposure resulted in lower levels of calcium required for activation than As(III) indicating an increased sensitivity to Ca(2+) after long term exposure to arsenate compared to arsenite. Myosin heavy chain and tropomyosin content in individual fibres was also decreased as a result of arsenic exposure. Single fibres exposed to As(V) produced significantly more force than muscle fibres from control animals. Long-term exposure of yabbies to arsenic alters the contractile function of the two major fibre types in the chelae. Copyright © 2014 Elsevier B.V. All rights reserved.

New method for the direct determination of dissolved Fe(III) concentration in acid mine waters

USGS Publications Warehouse

To, T.B.; Nordstrom, D. Kirk; Cunningham, K.M.; Ball, J.W.; McCleskey, R. Blaine

1999-01-01

A new method for direct determination of dissolved Fe(III) in acid mine water has been developed. In most present methods, Fe(III) is determined by computing the difference between total dissolved Fe and dissolved Fe(II). For acid mine waters, frequently Fe(II) >> Fe(III); thus, accuracy and precision are considerably improved by determining Fe(III) concentration directly. The new method utilizes two selective ligands to stabilize Fe(III) and Fe(II), thereby preventing changes in Fe reduction-oxidation distribution. Complexed Fe(II) is cleanly removed using a silica-based, reversed-phase adsorbent, yielding excellent isolation of the Fe(III) complex. Iron(III) concentration is measured colorimetrically or by graphite furnace atomic absorption spectrometry (GFAAS). The method requires inexpensive commercial reagents and simple procedures that can be used in the field. Calcium(II), Ni(II), Pb(II), AI(III), Zn(II), and Cd(II) cause insignificant colorimetric interferences for most acid mine waters. Waters containing >20 mg of Cu/L could cause a colorimetric interference and should be measured by GFAAS. Cobalt(II) and Cr(III) interfere if their molar ratios to Fe(III) exceed 24 and 5, respectively. Iron(II) interferes when its concentration exceeds the capacity of the complexing ligand (14 mg/L). Because of the GFAAS elemental specificity, only Fe(II) is a potential interferent in the GFAAS technique. The method detection limit is 2 ??g/L (40 nM) using GFAAS and 20 ??g/L (0.4 ??M) by colorimetry.A new method for direct determination of dissolved Fe(III) in acid mine water has been developed. In most present methods, Fe(III) is determined by computing the difference between total dissolved Fe and dissolved Fe(II). For acid mine waters, frequently Fe(II)???Fe(III); thus, accuracy and precision are considerably improved by determining Fe(III) concentration directly. The new method utilizes two selective ligands to stabilize Fe(III) and Fe(II), thereby preventing changes in Fe reduction-oxidation distribution. Complexed Fe(II) is cleanly removed using a silica-based, reversed-phase adsorbent, yielding excellent isolation of the Fe(III) complex. Iron(III) concentration is measured colorimetrically or by graphite furnace atomic absorption spectrometry (GFAAS). The method requires inexpensive commercial reagents and simple procedures that can be used in the field. Calcium(II), Ni(II), Pb(II), Al(III), Zn(II), and Cd(II) cause insignificant colorimetric interferences for most acid mine waters. Waters containing >20 mg of Cu/L could cause a colorimetric interference and should be measured by GFAAS. Cobalt(II) and Cr(III) interfere if their molar ratios to Fe(III) exceed 24 and 5, respectively. Iron(II) interferes when its concentration exceeds the capacity of the complexing ligand (14 mg/L). Because of the GFAAS elemental specificity, only Fe(II) is a potential interferent in the GFAAS technique. The method detection limit is 2/??g/L (40 nM) using GFAAS and 20 ??g/L (0.4 ??M) by colorimetry.

Cardiovascular risk factors and cognitive function in adults 30-59 years of age (NHANES III).

PubMed

Pavlik, Valory N; Hyman, David J; Doody, Rachelle

2005-01-01

In the Third National Health and Nutrition Examination Survey (NHANES III), three measures of cognitive function [Simple Reaction Time Test (SRTT), Symbol Digit Substitution Test (SDST), and Serial Digit Learning Test (SDLT)] were administered to a half-sample of 3,385 adult men and nonpregnant women 30-59 years of age with no history of stroke. We used multiple linear regression analysis to determine whether there was an independent association between performance on each cognitive function measure and defined hypertension (HTN) alone, type 2 diabetes mellitus (DM) alone, and coexistent HTN and DM after adjustment for demographic and socioeconomic variables and selected health behaviors. After adjustment for the sociodemographic variables, the combination of HTN + DM, but not HTN alone or DM alone, was significantly associated with worse performance on the SRTT (p = 0.031) and the SDST (p = 0.011). A similar pattern was observed for SDLT performance, but the relationship did not reach statistical significance (p = 0.101). We conclude that HTN in combination with DM is associated with detectable cognitive decrements in persons under age 60.

Manganese-catalysed benzylic C(sp3)-H amination for late-stage functionalization

NASA Astrophysics Data System (ADS)

Clark, Joseph R.; Feng, Kaibo; Sookezian, Anasheh; White, M. Christina

2018-06-01

Reactions that directly install nitrogen into C-H bonds of complex molecules are significant because of their potential to change the chemical and biological properties of a given compound. Although selective intramolecular C-H amination reactions are known, achieving high levels of reactivity while maintaining excellent site selectivity and functional-group tolerance remains a challenge for intermolecular C-H amination. Here, we report a manganese perchlorophthalocyanine catalyst [MnIII(ClPc)] for intermolecular benzylic C-H amination of bioactive molecules and natural products that proceeds with unprecedented levels of reactivity and site selectivity. In the presence of a Brønsted or Lewis acid, the [MnIII(ClPc)]-catalysed C-H amination demonstrates unique tolerance for tertiary amine, pyridine and benzimidazole functionalities. Mechanistic studies suggest that C-H amination likely proceeds through an electrophilic metallonitrene intermediate via a stepwise pathway where C-H cleavage is the rate-determining step of the reaction. Collectively, these mechanistic features contrast with previous base-metal-catalysed C-H aminations and provide new opportunities for tunable selectivities.

Manganese-catalysed benzylic C(sp3)-H amination for late-stage functionalization.

PubMed

Clark, Joseph R; Feng, Kaibo; Sookezian, Anasheh; White, M Christina

2018-06-01

Reactions that directly install nitrogen into C-H bonds of complex molecules are significant because of their potential to change the chemical and biological properties of a given compound. Although selective intramolecular C-H amination reactions are known, achieving high levels of reactivity while maintaining excellent site selectivity and functional-group tolerance remains a challenge for intermolecular C-H amination. Here, we report a manganese perchlorophthalocyanine catalyst [MnIII(ClPc)] for intermolecular benzylic C-H amination of bioactive molecules and natural products that proceeds with unprecedented levels of reactivity and site selectivity. In the presence of a Brønsted or Lewis acid, the [MnIII(ClPc)]-catalysed C-H amination demonstrates unique tolerance for tertiary amine, pyridine and benzimidazole functionalities. Mechanistic studies suggest that C-H amination likely proceeds through an electrophilic metallonitrene intermediate via a stepwise pathway where C-H cleavage is the rate-determining step of the reaction. Collectively, these mechanistic features contrast with previous base-metal-catalysed C-H aminations and provide new opportunities for tunable selectivities.

Baseline measure of health-related quality of life (Functional Assessment of Cancer Therapy-Esophagus) is associated with overall survival in patients with esophageal cancer.

PubMed

Kidane, Biniam; Sulman, Joanne; Xu, Wei; Kong, Qin Quinn; Wong, Rebecca; Knox, Jennifer J; Darling, Gail E

2016-06-01

Functional Assessment of Cancer Therapy-Esophagus is a health-related quality of life instrument validated in patients with esophageal cancer. It is composed of a general component and an esophageal cancer subscale. Our objective was to determine whether the baseline Functional Assessment of Cancer Therapy-Esophagus and esophageal cancer subscale scores are associated with survival in patients with stage II and III cancer of the gastroesophageal junction or thoracic esophagus. Data from 4 prospective studies in Canadian academic hospitals were combined. These included consecutive patients with stage II and III esophageal cancer who received neoadjuvant therapy followed by surgery or chemoradiation/radiation alone. All patients completed baseline Functional Assessment of Cancer Therapy-Esophagus. Functional Assessment of Cancer Therapy-Esophagus and esophageal cancer subscale scores were dichotomized on the basis of median scores. Cox regression analyses were performed. There were 207 patients treated between 1996 and 2014. Mean age was 61 ± 10.6 years. Approximately 69.6% of patients (n = 144) had adenocarcinoma. All patients had more than 9 months of follow-up. In patients with stage II and III, 93 deaths were observed. When treated as continuous variables, baseline Functional Assessment of Cancer Therapy-Esophagus and esophageal cancer subscale were associated with survival with hazard ratios of 0.89 (95% confidence interval [CI], 0.81-0.96; P = .005) and 0.68 (95% CI, 0.56-0.82; P < .001), respectively. When dichotomized, they were also associated with survival with a hazard ratio of 0.58 (95% CI, 0.38-0.89; P = .01) and 0.43 (95% CI, 0.28-0.67; P < .001), respectively. In patients with stage II and III esophageal cancer being considered for therapy, higher baseline Functional Assessment of Cancer Therapy-Esophagus and esophageal cancer subscale were independently associated with longer survival, even after adjusting for age, stage, histology, and therapy received. Further study is needed, but Functional Assessment of Cancer Therapy-Esophagus may be useful as a prognostic tool to inform patient decision-making and patient selection criteria for studies. Copyright © 2016 The American Association for Thoracic Surgery. Published by Elsevier Inc. All rights reserved.

A combined high-field EPR and quantum chemical study on a weakly ferromagnetically coupled dinuclear Mn(III) complex. A complete analysis of the EPR spectrum beyond the strong coupling limit.

PubMed

Retegan, Marius; Collomb, Marie-Noëlle; Neese, Frank; Duboc, Carole

2013-01-07

The electronic and magnetic properties of polynuclear complexes, in particular the magnetic anisotropy (zero field splitting, ZFS), the leading term of the spin Hamiltonian (SH), are commonly analyzed in a global manner and no attempt is usually made to understand the various contributions to the anisotropy at the atomic scale. This is especially true in weakly magnetically coupled systems. The present study addresses this problem and investigates the local SH parameters using a methodology based on experimental measurements and theoretical calculations. This work focuses on the challenging mono μ-oxo bis μ-acetato dinuclear Mn(III) complex: [Mn(2)(III)(μ-O)(μ-OAc)(2)L(2)](PF(6))(2) (with L = trispyrrolidine-1,4,7-triazacyclononane) (1), which is particularly difficult for EPR spectroscopy because of its large magnetic anisotropy and the weak ferromagnetic interaction between the two Mn(III) ions. High field (up to 12 T) and high frequency (190-345 GHz) EPR experiments have been recorded for 1 between 5 and 50 K. These data have been analyzed by employing a complex Hamiltonian, which encompasses terms describing the local and inter-site interactions. Density functional theory and multireference correlated ab initio calculations have been used to estimate the ZFS of the Mn(III) ions (D(Mn) = +4.29 cm(-1), E(Mn)/D(Mn) = 0.19) and the Euler angles reflecting the relative orientation of the ZFS tensor for each Mn(III) (α = -52°, β = 28°, γ = 3°). This analysis allowed the accurate determination of the local parameters: D(Mn) = +4.50 cm(-1), E(Mn)/D(Mn) = 0.07, α = -35°, β = 23°, γ = 2°. The spin ladder approach has also been applied, but only the parameters of the ground spin state of 1 have been accurately determined (D(4) = +1.540 cm(-1), E(4)/D(4) = 0.107). This is not sufficient to allow for the determination of the local parameters. The validity and practical performance of both approaches have been discussed.

Preparation and characterisation of crystalline tris(acetylacetonato)Fe(III) films grown on p-Si substrate for dielectric applications

NASA Astrophysics Data System (ADS)

Dakhel, A. A.; Ali-Mohamed, A. Y.

2007-02-01

Thin tris(acetylacetonato)iron(III) films were prepared by sublimation in vacuum on glass and p-Si substrates. Then comprehensive studies of X-ray fluorescence (XRF), X-ray diffraction (XRD), optical absorption spectroscopy, AC-conductivity, and dielectric permittivity as a function of frequency and temperature have been performed. The prepared films show a polycrystalline of orthorhombic structure. The optical absorption spectrum of the film was identical with that of the bulk powder layer. For electrical measurements of the complex as insulator, sample in form of metal insulator semiconductor (MIS) structure was prepared and characterised by the measurement of the capacitance and AC-conductance as a function of gate voltage. From those measurements, the state density Dit at insulator/semiconductor interface and the density of the fixed charges in the complex film were determined. It was found that Dit was of order 1010 eV-1/cm2 and the surface charge density in the insulator film was of order 1010 cm-2. The frequency dependence of the electrical conductivity and dielectric properties of MIS structures were studied at room temperature. It was observed that the experimental data follow the correlated barrier-hopping (CBH) model, from which the fundamental absorption edge, the cut off hopping distance, and other parameters of the model were determined. It was found that the capacitance of the complex increases as temperature increases. Generally, the present study shows that the tris(acetylacetonato)iron(III) films grown on p-Si is a promising candidate for low-k dielectric applications, it displays low-k value around 2.0.

Alterations in intrinsic mitochondrial function with aging are fiber type-specific and do not explain differential atrophy between muscles.

PubMed

Picard, Martin; Ritchie, Darmyn; Thomas, Melissa M; Wright, Kathryn J; Hepple, Russell T

2011-12-01

To determine whether mitochondrial dysfunction is causally related to muscle atrophy with aging, we examined respiratory capacity, H(2) O(2) emission, and function of the mitochondrial permeability transition pore (mPTP) in permeabilized myofibers prepared from four rat muscles that span a range of fiber type and degree of age-related atrophy. Muscle atrophy with aging was greatest in fast-twitch gastrocnemius (Gas) muscle (-38%), intermediate in both the fast-twitch extensor digitorum longus (EDL) and slow-twitch soleus (Sol) muscles (-21%), and non-existent in adductor longus (AL) muscle (+47%). In contrast, indices of mitochondrial dysfunction did not correspond to this differential degree of atrophy. Specifically, despite higher protein expression for oxidative phosphorylation (oxphos) system in fast Gas and EDL, state III respiratory capacity per myofiber wet weight was unchanged with aging, whereas the slow Sol showed proportional decreases in oxphos protein, citrate synthase activity, and state III respiration. Free radical leak (H(2) O(2) emission per O(2) flux) under state III respiration was higher with aging in the fast Gas, whereas state II free radical leak was higher in the slow AL. Only the fast muscles had impaired mPTP function with aging, with lower mitochondrial calcium retention capacity in EDL and shorter time to mPTP opening in Gas and EDL. Collectively, our results underscore that the age-related changes in muscle mitochondrial function depend largely upon fiber type and are unrelated to the severity of muscle atrophy, suggesting that intrinsic changes in mitochondrial function are unlikely to be causally involved in aging muscle atrophy. © 2011 The Authors. Aging Cell © 2011 Blackwell Publishing Ltd/Anatomical Society of Great Britain and Ireland.

Complexation humic substances of soils with metal ions as the main way migration of matals from soil to water

NASA Astrophysics Data System (ADS)

Dinu, Marina

2013-04-01

Organic matter (OM) of natural waters can bind with the ions metals (IM) entering the system, thus reducing their toxic properties. OM in water consists predominantly (up to 80%) of humic acids (HA), represented by highmolecular, dyed, polyfunctional compounds. The natural-climatic zones feature various ratios of fulvic (FA) and humic acids. An important specific feature of metals as contamination elements is the fact that when they occur in the environment, their potential toxicity and bioavailability depend significantly on their speciation. In recent years, lakes have been continuously enriched in hazardous elements such as Pb, Cd, Al, and Cr on a global (regional) basis. The most important organic ligands are humic matter (HM) washed out from soils in water and metals occur in natural waters as free ions, simple complexes with inorganic and organic ligands, and mineral and organic particles of molecules and ions sorbed on the surface. The occurrence of soluble metal forms in natural waters depends on the presence of organic and inorganic anions. However, direct determinations are rather difficult. The goal was the calculation and analysis of the forms of metals in the system catchment basin, based on the chemical composition of the water body and the structural features of soil humic substances (HS).We used the following analytical techniques - leaching of humic substances from soil and sample preparation (Orlov DS, 1985), the functional characteristics of humic substances - spectral analysis methods, the definition of conditional stability constants of complexes - electrochemical methods of analysis. Our results show thet HAs of selected soil types are different in functions, and these differences effect substantially the complexing process. When analyzing the results obtained in the course of spectrometric investigation of HMs in selected soil types, we determined the following main HA characteristics: (1) predominance of oxygen bearing groups in HM of the northern taiga soils; (2) similar amounts of oxygen bearing fragments, hydrocarbon constituents, and nitrogen bearing components in the mixed forest zones; (3) occurrence of aromatic and aliphatic hydrocarbons in HM of steppe soils. The HM functional characteristics influence substantially the stability constants of complexes with metal ions and complex stoichiometry: Fe(III)>Cu(II)>Pb(II)>Al(III)>Co(II)>Ni(II)>Cd(II)>Zn(II)>Cr(III)>Mg(II)>Sr(II)>Ca(II)>Mn(II) - northern taiga soils; Cu(II)>Fe(III)>Al(III)>Ni(II)>Zn(II)>Pb(II)>Co(II)>Cd(II)>Sr(II)>Mn(II)>Cr(III)>Ca(II)>Mg(II) - mixed forest zones; Fe(III)>Cu(II)>Al(III)>Pb(II)>Ni(II)>Zn(II)>Co(II)>Ca(II)>Cd(II)>Sr(II)>Mg(II)>Cr(III)>Mn(II) - steppe soils. 1. T.I. Moiseenko, L.P. Kudryavtseva, and N.A. Gashkina, Scattered Element in Surface Land Waters: Technophility, Bioaccumulation, and Ecotoxicology (Nauka, Moscow, 2006) 2. G. M. Varshal, Ext. Abstr. Doct. Dis. Chem. (Inst. Geokh. Analit. Khim. RAN, Moscow, 1994).. 4. D.S. Orlov, Humic Acids (MGU, Moscow, 1986) 5. D.V. Kovalevsky, Ext. Abstr. Cand. Dis. Chem. (MGU, Moscow, 1998). 6. I.A. Linnik and B. I. Nabivanets, Metal Migration Forms in Surface Fresh Waters (Gidrometizdat, Leningrad, 1985) 7. Hartley, F., Burgess, C., and Alcoc, R., Solution Equilibria (Ellis Horwood, Chichester (UK), 1980). 8. Yu. Yu. Lur'e, Reference Book of Physicochemical Values (Nauka, Moscow, 2000)

Corynebacterium glutamicum MTCC 2745 immobilized on granular activated carbon/MnFe2O4 composite: A novel biosorbent for removal of As(III) and As(V) ions.

PubMed

Podder, M S; Majumder, C B

2016-11-05

The optimization of biosorption/bioaccumulation process of both As(III) and As(V) has been investigated by using the biosorbent; biofilm of Corynebacterium glutamicum MTCC 2745 supported on granular activated carbon/MnFe2O4 composite (MGAC). The presence of functional groups on the cell wall surface of the biomass that may interact with the metal ions was proved by FT-IR. To determine the most appropriate correlation for the equilibrium curves employing the procedure of the non-linear regression for curve fitting analysis, isotherm studies were performed for As(III) and As(V) using 30 isotherm models. The pattern of biosorption/bioaccumulation fitted well with Vieth-Sladek isotherm model for As(III) and Brouers-Sotolongo and Fritz-Schlunder-V isotherm models for As(V). The maximum biosorption/bioaccumulation capacity estimated using Langmuir model were 2584.668mg/g for As(III) and 2651.675mg/g for As(V) at 30°C temperature and 220min contact time. The results showed that As(III) and As(V) removal was strongly pH-dependent with an optimum pH value of 7.0. D-R isotherm studies specified that ion exchange might play a prominent role. Copyright © 2016 Elsevier B.V. All rights reserved.

Chronic aerobic exercise training attenuates aortic stiffening and endothelial dysfunction through preserving aortic mitochondrial function in aged rats.

PubMed

Gu, Qi; Wang, Bing; Zhang, Xiao-Feng; Ma, Yan-Ping; Liu, Jian-Dong; Wang, Xiao-Ze

2014-08-01

Aging leads to large vessel arterial stiffening and endothelial dysfunction, which are important determinants of cardiovascular risk. The aim of present work was to assess the effects of chronic aerobic exercise training on aortic stiffening and endothelial dysfunction in aged rats and investigate the underlying mechanism about mitochondrial function. Chronic aerobic exercise training attenuated aortic stiffening with age marked by reduced collagen concentration, increased elastin concentration and reduced pulse wave velocity (PWV), and prevented aging-related endothelial dysfunction marked by improved endothelium-mediated vascular relaxation of aortas in response to acetylcholine. Chronic aerobic exercise training abated oxidative stress and nitrosative stress in aortas of aged rats. More importantly, we found that chronic aerobic exercise training in old rats preserved aortic mitochondrial function marked by reduced reactive oxygen species (ROS) formation and mitochondrial swelling, increased ATP formation and mitochondrial DNA content, and restored activities of complexes I and III and electron-coupling capacity between complexes I and III and between complexes II and III. In addition, it was found that chronic aerobic exercise training in old rats enhanced protein expression of uncoupling protein 2 (UCP-2), peroxisome proliferator-activated receptor γ co-activator 1α (PGC-1α), manganese superoxide dismutase (Mn-SOD), aldehyde dehydrogenase 2 (ALDH-2), prohibitin (PHB) and AMP-activated kinase (AMPK) phosphorylation in aortas. In conclusion, chronic aerobic exercise training preserved mitochondrial function in aortas, which, at least in part, explained the aorta-protecting effects of exercise training in aging. Copyright © 2014 Elsevier Inc. All rights reserved.

Food safety security: a new concept for enhancing food safety measures.

PubMed

Iyengar, Venkatesh; Elmadfa, Ibrahim

2012-06-01

The food safety security (FSS) concept is perceived as an early warning system for minimizing food safety (FS) breaches, and it functions in conjunction with existing FS measures. Essentially, the function of FS and FSS measures can be visualized in two parts: (i) the FS preventive measures as actions taken at the stem level, and (ii) the FSS interventions as actions taken at the root level, to enhance the impact of the implemented safety steps. In practice, along with FS, FSS also draws its support from (i) legislative directives and regulatory measures for enforcing verifiable, timely, and effective compliance; (ii) measurement systems in place for sustained quality assurance; and (iii) shared responsibility to ensure cohesion among all the stakeholders namely, policy makers, regulators, food producers, processors and distributors, and consumers. However, the functional framework of FSS differs from that of FS by way of: (i) retooling the vulnerable segments of the preventive features of existing FS measures; (ii) fine-tuning response systems to efficiently preempt the FS breaches; (iii) building a long-term nutrient and toxicant surveillance network based on validated measurement systems functioning in real time; (iv) focusing on crisp, clear, and correct communication that resonates among all the stakeholders; and (v) developing inter-disciplinary human resources to meet ever-increasing FS challenges. Important determinants of FSS include: (i) strengthening international dialogue for refining regulatory reforms and addressing emerging risks; (ii) developing innovative and strategic action points for intervention {in addition to Hazard Analysis and Critical Control Points (HACCP) procedures]; and (iii) introducing additional science-based tools such as metrology-based measurement systems.

Luminescence Properties of Self-Aggregating TbIII-DOTA-Functionalized Calix[4]arenes

NASA Astrophysics Data System (ADS)

Mayer, Florian; Tiruvadi Krishnan, Sriram; Schühle, Daniel T.; Eliseeva, Svetlana V.; Petoud, Stéphane; Tóth, Éva; Djanashvili, Kristina

2018-01-01

Self-aggregating calix[4]arenes carrying four DOTA ligands on the upper rim for stable complexation of paramagnetic GdIII-ions have already been proposed as MRI probes. In this work, we investigate the luminescence properties of TbIII-DOTA-calix[4]arene-4OPr containing four propyl-groups and compare them with those of the analogue substituted with a phthalimide chromophore (TbIII-DOTA-calix[4]arene-3OPr-OPhth). We show that, given its four aromatic rings, the calix[4]arene core acts as an effective sensitizer of Tb-centered luminescence. Substituents on the lower rim can modulate the aggregation behavior, which in turn determines the luminescence properties of the compounds. In solid state, the quantum yield of the phthalimide derivative is almost three times as high as that of the propyl-functionalized analogue demonstrating a beneficial role of the chromophore on Tb-luminescence. In solution, however, the effect of the phthalimide group vanishes, which we attribute to the large distance between the chromophore and the lanthanide, situated on the opposite rims of the calix[4]arene. Both quantum yields and luminescence lifetimes show clear concentration dependence in solution, related to the strong impact of aggregation on the luminescence behaviour. We also evidence the variability in the values of the critical micelle concentration depending on the experimental technique. Such luminescent calix[4]arene platforms accommodating stable lanthanide complexes can be considered valuable building blocks for the design of dual MR/optical imaging probes.

Luminescence Properties of Self-Aggregating TbIII-DOTA-Functionalized Calix[4]arenes.

PubMed

Mayer, Florian; Tiruvadi Krishnan, Sriram; Schühle, Daniel T; Eliseeva, Svetlana V; Petoud, Stéphane; Tóth, Éva; Djanashvili, Kristina

2018-01-01

Self-aggregating calix[4]arenes carrying four DOTA ligands on the upper rim for stable complexation of paramagnetic Gd III -ions have already been proposed as MRI probes. In this work, we investigate the luminescence properties of Tb III -DOTA-calix[4]arene-4OPr containing four propyl-groups and compare them with those of the analog substituted with a phthalimide chromophore (Tb III -DOTA-calix[4]arene-3OPr-OPhth). We show that, given its four aromatic rings, the calix[4]arene core acts as an effective sensitizer of Tb-centered luminescence. Substituents on the lower rim can modulate the aggregation behavior, which in turn determines the luminescence properties of the compounds. In solid state, the quantum yield of the phthalimide derivative is almost three times as high as that of the propyl-functionalized analog demonstrating a beneficial role of the chromophore on Tb-luminescence. In solution, however, the effect of the phthalimide group vanishes, which we attribute to the large distance between the chromophore and the lanthanide, situated on the opposite rims of the calix[4]arene. Both quantum yields and luminescence lifetimes show clear concentration dependence in solution, related to the strong impact of aggregation on the luminescence behavior. We also evidence the variability in the values of the critical micelle concentration depending on the experimental technique. Such luminescent calix[4]arene platforms accommodating stable lanthanide complexes can be considered valuable building blocks for the design of dual MR/optical imaging probes.

A Quantitative Study of the Relationship between the Distribution of Different Types of Collagen and the Mechanical Behavior of Rabbit Medial Collateral Ligaments

PubMed Central

Wan, Chao; Hao, Zhixiu; Wen, Shizhu; Leng, Huijie

2014-01-01

The mechanical properties of ligaments are key contributors to the stability and function of musculoskeletal joints. Ligaments are generally composed of ground substance, collagen (mainly type I and III collagen), and minimal elastin fibers. However, no consensus has been reached about whether the distribution of different types of collagen correlates with the mechanical behaviors of ligaments. The main objective of this study was to determine whether the collagen type distribution is correlated with the mechanical properties of ligaments. Using axial tensile tests and picrosirius red staining-polarization observations, the mechanical behaviors and the ratios of the various types of collagen were investigated for twenty-four rabbit medial collateral ligaments from twenty-four rabbits of different ages, respectively. One-way analysis of variance was used in the comparison of the Young's modulus in the linear region of the stress-strain curves and the ratios of type I and III collagen for the specimens (the mid-substance specimens of the ligaments) with different ages. A multiple linear regression was performed using the collagen contents (the ratios of type I and III collagen) and the Young's modulus of the specimens. During the maturation of the ligaments, the type I collagen content increased, and the type III collagen content decreased. A significant and strong correlation () was identified by multiple linear regression between the collagen contents (i.e., the ratios of type I and type III collagen) and the mechanical properties of the specimens. The collagen content of ligaments might provide a new perspective for evaluating the linear modulus of global stress-strain curves for ligaments and open a new door for studying the mechanical behaviors and functions of connective tissues. PMID:25062068

A quantitative study of the relationship between the distribution of different types of collagen and the mechanical behavior of rabbit medial collateral ligaments.

PubMed

Wan, Chao; Hao, Zhixiu; Wen, Shizhu; Leng, Huijie

2014-01-01

The mechanical properties of ligaments are key contributors to the stability and function of musculoskeletal joints. Ligaments are generally composed of ground substance, collagen (mainly type I and III collagen), and minimal elastin fibers. However, no consensus has been reached about whether the distribution of different types of collagen correlates with the mechanical behaviors of ligaments. The main objective of this study was to determine whether the collagen type distribution is correlated with the mechanical properties of ligaments. Using axial tensile tests and picrosirius red staining-polarization observations, the mechanical behaviors and the ratios of the various types of collagen were investigated for twenty-four rabbit medial collateral ligaments from twenty-four rabbits of different ages, respectively. One-way analysis of variance was used in the comparison of the Young's modulus in the linear region of the stress-strain curves and the ratios of type I and III collagen for the specimens (the mid-substance specimens of the ligaments) with different ages. A multiple linear regression was performed using the collagen contents (the ratios of type I and III collagen) and the Young's modulus of the specimens. During the maturation of the ligaments, the type I collagen content increased, and the type III collagen content decreased. A significant and strong correlation (R2 = 0.839, P < 0.05) was identified by multiple linear regression between the collagen contents (i.e., the ratios of type I and type III collagen) and the mechanical properties of the specimens. The collagen content of ligaments might provide a new perspective for evaluating the linear modulus of global stress-strain curves for ligaments and open a new door for studying the mechanical behaviors and functions of connective tissues.

Design principles and theory of paramagnetic fluorine-labelled lanthanide complexes as probes for (19)F magnetic resonance: a proof-of-concept study.

PubMed

Chalmers, Kirsten H; De Luca, Elena; Hogg, Naomi H M; Kenwright, Alan M; Kuprov, Ilya; Parker, David; Botta, Mauro; Wilson, J Ian; Blamire, Andrew M

2010-01-04

The synthesis and spectroscopic properties of a series of CF(3)-labelled lanthanide(III) complexes (Ln=Gd, Tb, Dy, Ho, Er, Tm) with amide-substituted ligands based on 1,4,7,10-tetraazacyclododecane are described. The theoretical contributions of the (19)F magnetic relaxation processes in these systems are critically assessed and selected volumetric plots are presented. These plots allow an accurate estimation of the increase in the rates of longitudinal and transverse relaxation as a function of the distance between the Ln(III) ion and the fluorine nucleus, the applied magnetic field, and the re-rotational correlation time of the complex, for a given Ln(III) ion. Selected complexes exhibit pH-dependent chemical shift behaviour, and a pK(a) of 7.0 was determined in one example based on the holmium complex of an ortho-cyano DO3A-monoamide ligand, which allowed the pH to be assessed by measuring the difference in chemical shift (varying by over 14 ppm) between two (19)F resonances. Relaxation analyses of variable-temperature and variable-field (19)F, (17)O and (1)H NMR spectroscopy experiments are reported, aided by identification of salient low-energy conformers by using density functional theory. The study of fluorine relaxation rates, over a field range of 4.7 to 16.5 T allowed precise computation of the distance between the Ln(III) ion and the CF(3) reporter group by using global fitting methods. The sensitivity benefits of using such paramagnetic fluorinated probes in (19)F NMR spectroscopic studies are quantified in preliminary spectroscopic and imaging experiments with respect to a diamagnetic yttrium(III) analogue.

Functional analysis of the missense APOC3 mutation Ala23Thr associated with human hypotriglyceridemia.

PubMed

Sundaram, Meenakshi; Zhong, Shumei; Bou Khalil, Maroun; Zhou, Hu; Jiang, Zhenghui G; Zhao, Yang; Iqbal, Jahangir; Hussain, M Mahmood; Figeys, Daniel; Wang, Yuwei; Yao, Zemin

2010-06-01

We have shown that expression of apolipoprotein (apo) C-III promotes VLDL secretion from transfected McA-RH7777 cells under lipid-rich conditions. To determine structural elements within apoC-III that confer to this function, we contrasted wild-type apoC-III with a mutant Ala23Thr originally identified in hypotriglyceridemia subjects. Although synthesis of [(3)H]glycerol-labeled TAG was comparable between cells expressing wild-type apoC-III (C3wt cells) or Ala23Thr mutant (C3AT cells), secretion of [(3)H]TAG from C3AT cells was markedly decreased. The lowered [(3)H]TAG secretion was associated with an inability of C3AT cells to assemble VLDL(1). Moreover, [(3)H]TAG within the microsomal lumen in C3AT cells was 60% higher than that in C3wt cells, yet the activity of microsomal triglyceride-transfer protein in C3AT cells was not elevated. The accumulated [(3)H]TAG in C3AT microsomal lumen was mainly associated with lumenal IDL/LDL-like lipoproteins. Phenotypically, this [(3)H]TAG fractionation profiling resembled what was observed in cells treated with brefeldin A, which at low dose specifically blocked the second-step VLDL(1) maturation. Furthermore, lumenal [(35)S]Ala23Thr protein accumulated in IDL/LDL fractions and was absent in VLDL fractions in C3AT cells. These results suggest that the presence of Ala23Thr protein in lumenal IDL/LDL particles might prevent effective fusion between lipid droplets and VLDL precursors. Thus, the current study reveals an important structural element residing within the N-terminal region of apoC-III that governs the second step VLDL(1) maturation.

Discriminating the reaction types of plant type III polyketide synthases

PubMed Central

Shimizu, Yugo; Ogata, Hiroyuki; Goto, Susumu

2017-01-01

Abstract Motivation: Functional prediction of paralogs is challenging in bioinformatics because of rapid functional diversification after gene duplication events combined with parallel acquisitions of similar functions by different paralogs. Plant type III polyketide synthases (PKSs), producing various secondary metabolites, represent a paralogous family that has undergone gene duplication and functional alteration. Currently, there is no computational method available for the functional prediction of type III PKSs. Results: We developed a plant type III PKS reaction predictor, pPAP, based on the recently proposed classification of type III PKSs. pPAP combines two kinds of similarity measures: one calculated by profile hidden Markov models (pHMMs) built from functionally and structurally important partial sequence regions, and the other based on mutual information between residue positions. pPAP targets PKSs acting on ring-type starter substrates, and classifies their functions into four reaction types. The pHMM approach discriminated two reaction types with high accuracy (97.5%, 39/40), but its accuracy decreased when discriminating three reaction types (87.8%, 43/49). When combined with a correlation-based approach, all 49 PKSs were correctly discriminated, and pPAP was still highly accurate (91.4%, 64/70) even after adding other reaction types. These results suggest pPAP, which is based on linear discriminant analyses of similarity measures, is effective for plant type III PKS function prediction. Availability and Implementation: pPAP is freely available at ftp://ftp.genome.jp/pub/tools/ppap/ Contact: goto@kuicr.kyoto-u.ac.jp Supplementary information: Supplementary data are available at Bioinformatics online. PMID:28334262

Theory of inhomogeneous quantum systems. III. Variational wave functions for Fermi fluids

NASA Astrophysics Data System (ADS)

Krotscheck, E.

1985-04-01

We develop a general variational theory for inhomogeneous Fermi systems such as the electron gas in a metal surface, the surface of liquid 3He, or simple models of heavy nuclei. The ground-state wave function is expressed in terms of two-body correlations, a one-body attenuation factor, and a model-system Slater determinant. Massive partial summations of cluster expansions are performed by means of Born-Green-Yvon and hypernetted-chain techniques. An optimal single-particle basis is generated by a generalized Hartree-Fock equation in which the two-body correlations screen the bare interparticle interaction. The optimization of the pair correlations leads to a state-averaged random-phase-approximation equation and a strictly microscopic determination of the particle-hole interaction.

Influence of Al(III) on biofilm and its extracellular polymeric substances in sequencing batch biofilm reactors.

PubMed

Hu, Xuewei; Yang, Lei; Lai, Xinke; Yao, Qi; Chen, Kai

2017-10-03

This paper presented the influence of Al(III) on biodegradability, micromorphology, composition and functional groups characteristics of the biofilm extracellular polymeric substances (EPS) during different growth phases. The sequencing batch biofilm reactors were developed to cultivate biofilms under different Al(III) dosages. The results elucidated that Al(III) affected biofilm development adversely at the beginning of biofilm growth, but promoted the biofilm mass and improved the biofilm activity with the growth of the biofilm. The micromorphological observation indicated that Al(III) led to a reduction of the filaments and promotion of the EPS secretion in growth phases of the biofilm, also Al(III) could promote microorganisms to form larger colonies for mature biofilm. Then, the analysis of EPS contents and components suggested that Al(III) could increase the protein (PN) of tightly bound EPS (TB-EPS) which alleviated the metal toxicity inhibition on the biofilm during the initial phases of biofilm growth. The biofilm could gradually adapt to the inhibition caused by Al(III) at the biofilm maturation moment. Finally, through the Fourier transform infrared spectroscopy, it was found that Al(III) was beneficial for the proliferation and secretion of TB-EPS functional groups, especially the functional groups of protein and polysaccharides.

α-synuclein and synapsin III cooperatively regulate synaptic function in dopamine neurons.

PubMed

Zaltieri, Michela; Grigoletto, Jessica; Longhena, Francesca; Navarria, Laura; Favero, Gaia; Castrezzati, Stefania; Colivicchi, Maria Alessandra; Della Corte, Laura; Rezzani, Rita; Pizzi, Marina; Benfenati, Fabio; Spillantini, Maria Grazia; Missale, Cristina; Spano, PierFranco; Bellucci, Arianna

2015-07-01

The main neuropathological features of Parkinson's disease are dopaminergic nigrostriatal neuron degeneration, and intraneuronal and intraneuritic proteinaceous inclusions named Lewy bodies and Lewy neurites, respectively, which mainly contain α-synuclein (α-syn, also known as SNCA). The neuronal phosphoprotein synapsin III (also known as SYN3), is a pivotal regulator of dopamine neuron synaptic function. Here, we show that α-syn interacts with and modulates synapsin III. The absence of α-syn causes a selective increase and redistribution of synapsin III, and changes the organization of synaptic vesicle pools in dopamine neurons. In α-syn-null mice, the alterations of synapsin III induce an increased locomotor response to the stimulation of synapsin-dependent dopamine overflow, despite this, these mice show decreased basal and depolarization-dependent striatal dopamine release. Of note, synapsin III seems to be involved in α-syn aggregation, which also coaxes its increase and redistribution. Furthermore, synapsin III accumulates in the caudate and putamen of individuals with Parkinson's disease. These findings support a reciprocal modulatory interaction of α-syn and synapsin III in the regulation of dopamine neuron synaptic function. © 2015. Published by The Company of Biologists Ltd.

Quantum chemical study of arsenic (III, V) adsorption on Mn-oxides: implications for arsenic(III) oxidation.

PubMed

Zhu, Mengqiang; Paul, Kristian W; Kubicki, James D; Sparks, Donald L

2009-09-01

Density functional theory (DFT) calculations were used to investigate As(V) and As(III) surface complex structures and reaction energies on both Mn(III) and Mn(IV) sites in an attempt to better understand As(III) oxidation bybirnessite, a layered Mn-dioxide mineral. Edge-sharing dioctahedral Mn(III) and Mn(IV) clusters with different combinations of surface functional groups (>MnOH and >MnOH2) were employed to mimic pH variability. Results show that As(V) adsorption was more thermodynamically favorable than As(III) adsorption on both Mn(III) and Mn(IV) surface sites under simulated acidic pH conditions. Therefore, we propose that As(V) adsorption inhibits As(III) oxidation by blocking adsorption sites. Under simulated acidic pH conditions, Mn(IV) sites exhibited stronger adsorption affinity than Mn(III) sites for both As(III) and As(V). Overall, we hypothesize that Mn(III) sites are less reactive in terms of As(III) oxidation due to their lower affinity for As(III) adsorption, higher potential to be blocked by As(V) complexes, and slower electron transfer rates with adsorbed As(III). Results from this study offer an explanation regarding the experimental observations of Mn(III) accumulation on birnessite and the long residence time of As(III) adsorption complexes on manganite (r-MnOOH) during As(III) oxidation.

Theoretical study of the magnetic exchange coupling behavior substituting Cr(III) with Mo(III) in cyano-bridged transition metal complexes

NASA Astrophysics Data System (ADS)

Zhang, Yi-Quan; Luo, Cheng-Lin

Molecular magnetism in a series of cyano-bridged first and second transition metal complexes has been investigated using density functional theory (DFT) combined with the broken-symmetry (BS) approach. Several exchange-correlation (XC) functionals in the ADF package were used to investigate complexes I [-(Me3tacn)2(cyclam)NiMo2(CN)6]2+, II [-(Me3tacn)2(cyclam)Ni-Cr2(CN)6]2+, III [(Me3tacn)6MnMo6(CN)18]2+, and IV [(Me3tacn)6MnCr6(CN)18]2+ (Me3tacn = N,N?,N‴-trimethyl-1,4,7-triazacyclononane). For models A (the molded structure of complex I) and B (the modeled structure of complex II), all the XCs given qualitatively reasonable results and predict ferromagnetic coupling character between M (M = MoIII for A or CrIII for B) and NiII in coincidence with the experimental results (see Tables and ). The calculated using Operdew, OPBE, O3LYP, and B3LYP functionals and experimental J values show that substituting CrIII with MoIII will enhance the ferromagnetic exchange coupling interactions. But VWN, PW91, PBE, VSXC, and tau-HCTH functionals have no way to differentiate the relative strength of the intramolecular magnetic exchange coupling interactions of A and B correctly. For models C (the modeled structure of complex III) and D (the modeled structure of complex IV), all the XCs in ADF and B3LYP in Gaussian 03 with several basis sets show that substituting CrIII with MoIII will enhance the antiferromagnetic exchange coupling interactions. From the above calculations, the substitution of CrIII by MoIII will enhance the magnetic coupling interactions, whether the magnetic coupling interactions are ferro- or antiferromagnetic. Moreover, Kahn's model was applied to investigate the above facts.

Functional redundancy and sensitivity of fish assemblages in European rivers, lakes and estuarine ecosystems.

PubMed

Teichert, Nils; Lepage, Mario; Sagouis, Alban; Borja, Angel; Chust, Guillem; Ferreira, Maria Teresa; Pasquaud, Stéphanie; Schinegger, Rafaela; Segurado, Pedro; Argillier, Christine

2017-12-14

The impact of species loss on ecosystems functioning depends on the amount of trait similarity between species, i.e. functional redundancy, but it is also influenced by the order in which species are lost. Here we investigated redundancy and sensitivity patterns across fish assemblages in lakes, rivers and estuaries. Several scenarios of species extinction were simulated to determine whether the loss of vulnerable species (with high propensity of extinction when facing threats) causes a greater functional alteration than random extinction. Our results indicate that the functional redundancy tended to increase with species richness in lakes and rivers, but not in estuaries. We demonstrated that i) in the three systems, some combinations of functional traits are supported by non-redundant species, ii) rare species in rivers and estuaries support singular functions not shared by dominant species, iii) the loss of vulnerable species can induce greater functional alteration in rivers than in lakes and estuaries. Overall, the functional structure of fish assemblages in rivers is weakly buffered against species extinction because vulnerable species support singular functions. More specifically, a hotspot of functional sensitivity was highlighted in the Iberian Peninsula, which emphasizes the usefulness of quantitative criteria to determine conservation priorities.

Redo surgery risk in patients with cardiac prosthetic valve dysfunction

PubMed Central

Maciejewski, Marek; Piestrzeniewicz, Katarzyna; Bielecka-Dąbrowa, Agata; Piechowiak, Monika; Jaszewski, Ryszard

2011-01-01

Introduction The aim of the study was to analyse the risk factors of early and late mortality in patients undergoing the first reoperation for prosthetic valve dysfunction. Material and methods A retrospective observational study was performed in 194 consecutive patients (M = 75, F = 119; mean age 53.2 ±11 years) with a mechanical prosthetic valve (n = 103 cases; 53%) or bioprosthesis (91; 47%). Univariate and multivariate Cox statistical analysis was performed to determine risk factors of early and late mortality. Results The overall early mortality was 18.6%: 31.4% in patients with symptoms of NYHA functional class III-IV and 3.4% in pts in NYHA class I-II. Multivariate analysis identified symptoms of NYHA class III-IV and endocarditis as independent predictors of early mortality. The overall late mortality (> 30 days) was 8.2% (0.62% year/patient). Multivariate analysis identified age at the time of reoperation as a strong independent predictor of late mortality. Conclusions Reoperation in patients with prosthetic valves, performed urgently, especially in patients with symptoms of NYHA class III-IV or in the case of endocarditis, bears a high mortality rate. Risk of planned reoperation, mostly in patients with symptoms of NYHA class I-II, does not differ from the risk of the first operation. PMID:22291767

Discriminant Value of Rome III Questionnaire in Dyspeptic Patients

PubMed Central

Abid, Shahab; Siddiqui, Shaheryar; Jafri, Wasim

2011-01-01

Background/Aim: Rome III criteria has modified the description of functional dyspepsia (FD) and divided this into subgroups. However, the discriminative value of Rome III questionnaire-based diagnosis of FD is yet to be determined. Objectives: To evaluate the Rome III questionnaire for the diagnosis of FD and whether it can discriminate between postprandial distress syndrome (PDS) and epigastric pain syndrome (EPS) in patients with dyspeptic symptoms. Patients and Methods: Consecutive patients, who were not on proton pump inhibitors (PPI), were asked to participate. Patients who have previously established acid peptic disease or predominantly reflux symptoms or having alarm symptoms such as weight loss and hematemesis were excluded. Rome III questionnaire for FD was used to identify the patients as having FD and divide into its subgroups; PDS or EPS. Gastro-duodenal biopsies, liver function tests and ultrasound were done to establish the diagnosis of FD. Results: Out of 272 patients with upper gastrointestinal (GI) symptoms without alarm features, who were enrolled in the study, a total of 191 (70%) fulfilled the criteria of FD based upon Rome III questionnaire. EPS subgroup was found in 109 (57%), PDS in 17 (9%) patients, overlap between EPS and PDS was present in 56 (29%) patients. Nine (5%) patients remained indeterminate. Diagnosis of FD was established in 136/191 (71%) patients only. Gastritis was present in 116 patients (85%), Duodenitis in 44 (32%) and Helicobacter pylori infection in 70 (51%) patients. Among 55 patients (29%) who had organic diseases, EPS was seen in 35 (64%), PDS in 5 (9%) and overlap in 15 (27%) patients. Underlying organic causes were gastric or duodenal ulcers in 14 patients, Barrett esophagus in five, chronic liver disease in seven, gall stones in five, Giardiasis and celiac disease in three each. Gastric carcinoma, Crohns disease and gastric polyps were seen in one patient each. Conclusion: This study indicates that 30% of patients who fulfilled the Rome III criteria for FD actually had organic disease. Almost one-third of patients with functioanl dyspepsia did not qualify for one of the two subgroups of FD of Rome III. There is also a need to further define the Rome III-based subgroups of FD for research purpose. PMID:21372351

A Short Note on the Scaling Function Constant Problem in the Two-Dimensional Ising Model

NASA Astrophysics Data System (ADS)

Bothner, Thomas

2018-02-01

We provide a simple derivation of the constant factor in the short-distance asymptotics of the tau-function associated with the 2-point function of the two-dimensional Ising model. This factor was first computed by Tracy (Commun Math Phys 142:297-311, 1991) via an exponential series expansion of the correlation function. Further simplifications in the analysis are due to Tracy and Widom (Commun Math Phys 190:697-721, 1998) using Fredholm determinant representations of the correlation function and Wiener-Hopf approximation results for the underlying resolvent operator. Our method relies on an action integral representation of the tau-function and asymptotic results for the underlying Painlevé-III transcendent from McCoy et al. (J Math Phys 18:1058-1092, 1977).

Thermometric studies on the Fe(III)-EDTA chelate.

PubMed

Dot, K

1978-02-01

A DeltaH of -11.5 +/- 0.5 kJ/mole has been determined for the formation of the Fe(III)-EDTA chelate at 25.0 degrees and mu = 0.1(= [HClO(4)] + [NaClO(4)]) by a direct thermometric titration procedure. The entropy change, DeltaS, has been calculated to be 440 J.mole(-1) .deg(-1) by combining the result of the heat measurements with the free energy change obtained from the stability constant previously determined. A relationship between the DeltaS values and the standard partial molal entropies of the tervalent metal ions is discussed. In addition, conditions for the thermometric titration of Fe(III) with NA(4)EDTA at room temperature have been investigated. Iron(III) can be determined in the presence of fairly large amounts of phosphate, Cr(III), Mn(II) and Al(III).

Construct Validity of the Chinese Version of the Activities of Daily Living Rating Scale III in Patients with Schizophrenia

PubMed Central

Chiu, En-Chi; Lee, Yen; Lai, Kuan-Yu; Kuo, Chian-Jue; Lee, Shu-Chun; Hsieh, Ching-Lin

2015-01-01

Background The Chinese version of the Activities of Daily Living Rating Scale III (ADLRS-III), which has 10 domains, is commonly used for assessing activities of daily living (ADL) in patients with schizophrenia. However, construct validity (i.e., unidimensionality) for each domain of the ADLRS-III is unknown, limiting the explanations of the test results. Purpose This main purpose of this study was to examine unidimensionality of each domain in the ADLRS-III. We also examined internal consistency and ceiling/floor effects in patients with schizophrenia. Methods From occupational therapy records, we obtained 304 self-report data of the ADLRS-III. Confirmatory factor analysis (CFA) was conducted to examine the 10 one-factor structures. If a domain showed an insufficient model fit, exploratory factor analysis (EFA) was performed to investigate the factor structure and choose one factor representing the original construct. Internal consistency was examined using Cronbach’s alpha (α). Ceiling and floor effects were determined by the percentage of patients with the maximum and minimum scores in each domain, respectively. Results CFA analyses showed that 4 domains (i.e., leisure, picture recognition, literacy ability, communication tools use) had sufficient model fits. These 4 domains had acceptable internal consistency (α = 0.79-0.87) and no ceiling/floor effects, except the leisure domain which had a ceiling effect. The other 6 domains showed insufficient model fits. The EFA results showed that these 6 domains were two-factor structures. Conclusion The results supported unidimensional constructs of the leisure, picture recognition, literacy ability, and communication tool uses domains. The sum scores of these 4 domains can be used to represent their respective domain-specific functions. Regarding the 6 domains with insufficient model fits, we have explained the two factors of each domain and chosen one factor to represent its original construct. Future users may use the items from the chosen factors to assess domain-specific functions in patients with schizophrenia. PMID:26121246

Screening for cognitive and behavioural impairment in amyotrophic lateral sclerosis: Frequency of abnormality and effect on survival.

PubMed

Xu, Zhouwei; Alruwaili, Ashwag Rafea S; Henderson, Robert David; McCombe, Pamela Ann

2017-05-15

To screen for cognitive and behavioural impairment in people with amyotrophic lateral sclerosis (ALS) and controls with neuromuscular disease and to correlate these with clinical features. 108 people with ALS and 60 controls with other neuromuscular diseases were recruited and assessed with the Addenbrooke's cognitive examination-III (ACE-III), the frontal assessment battery (FAB), and the executive function component of the Edinburgh cognitive and behavioural ALS screen (ECAS). The Amyotrophic lateral sclerosis-Frontotemporal dementia questionnaire (ALS-FTD-Q) and the Motor Neuron Disease Behavioural instrument (MiND-B) were administered to the caregivers of people with ALS. The prevalence of abnormalities was determined and correlated with clinical features and survival. In 37 people with ALS, serial studies were performed. The frequencies of cognitive impairment based on the ACE-III and FAB were 30.0% and 14.0%, in ALS and 11.7% and 3.3% in controls, respectively. Age and years of education influence the results of the ACE-III and ECAS executive function. In ALS, the frequencies of behavioural impairment based on ALS-FTD-Q and MiND-B were 32.1% and 39.4%, respectively. There is significant correlation of ALS-FTD-Q and MiND-B with the ALSFRS-R score. ALS participants with cognitive impairment measured with ACE-III had significantly shorter survival time than those without. ALS participants with behavioural impairment measured with ALS-FTD-Q had worse prognosis than those without. No significant difference was found between the first two serial cognitive tests based on ACE-III and FAB by using generalized estimating equation. There is a greater frequency of cognitive impairment in people with ALS than in patients with other neuromuscular diseases. The cognitive and behavioural tests are potential biomarkers of the prognosis of ALS. The results of cognitive tests are stable over 6months and possibly longer. Copyright © 2017 Elsevier B.V. All rights reserved.

Spectrophotometric Determination of Iron(III)-Glycine Formation Constant in Aqueous Medium Using Competitive Ligand Binding

ERIC Educational Resources Information Center

Prasad, Rajendra; Prasad, Surendra

2009-01-01

The formation constant of iron(III) complex with glycine (Gly) ligand in aqueous acidic medium (0.2 M HNO[subscript 3], I = 0.2 M at 28 plus or minus 1 degree C) was determined spectrophotometrically in which a competing color reaction between Fe(III) and SCN[superscript -] was used as an indicator reaction. Under the specified conditions Fe(III)…

New onset of constipation during long-term physical inactivity: a proof-of-concept study on the immobility-induced bowel changes.

PubMed

Iovino, Paola; Chiarioni, Giuseppe; Bilancio, Giancarlo; Cirillo, Massimo; Mekjavic, Igor B; Pisot, Rado; Ciacci, Carolina

2013-01-01

The pathophysiological mechanisms underlining constipation are incompletely understood, but prolonged bed rest is commonly considered a relevant determinant. Our primary aim was to study the effect of long-term physical inactivity on determining a new onset of constipation. Secondary aim were the evaluation of changes in stool frequency, bowel function and symptoms induced by this prolonged physical inactivity. Ten healthy men underwent a 7-day run-in followed by 35-day study of experimentally-controlled bed rest. The study was sponsored by the Italian Space Agency. The onset of constipation was evaluated according to Rome III criteria for functional constipation. Abdominal bloating, flatulence, pain and urgency were assessed by a 100mm Visual Analog Scales and bowel function by adjectival scales (Bristol Stool Form Scale, ease of passage of stool and sense of incomplete evacuation). Daily measurements of bowel movements was summarized on a weekly score. Pre and post bed rest Quality of Life (SF-36), general health (Goldberg's General Health) and depression mood (Zung scale) questionnaires were administered. New onset of functional constipation fulfilling Rome III criteria was found in 60% (6/10) of participants (p=0.03). The score of flatulence significantly increased whilst the stool frequency significantly decreased during the week-by-week comparisons period (repeated-measures ANOVA, p=0.02 and p=0.001, respectively). Stool consistency and bowel symptoms were not influenced by prolonged physical inactivity. In addition, no significant changes were observed in general health, in mood state and in quality of life at the end of bed rest. Our results provide evidence that prolonged physical inactivity is relevant etiology in functional constipation in healthy individuals. The common clinical suggestion of early mobilization in bedridden patients is supported as well.

Outcome assessments in children with cerebral palsy, part II: discriminatory ability of outcome tools.

PubMed

Bagley, Anita M; Gorton, George; Oeffinger, Donna; Barnes, Douglas; Calmes, Janine; Nicholson, Diane; Damiano, Diane; Abel, Mark; Kryscio, Richard; Rogers, Sarah; Tylkowski, Chester

2007-03-01

Discriminatory ability of several pediatric outcome tools was assessed relative to Gross Motor Function Classification System (GMFCS) level in patients with cerebral palsy. Five hundred and sixty-two patients (400 with diplegia, 162 with hemiplegia; 339 males, 223 females; age range 4-18y, mean 11y 1mo [SD 3y 7mo]), classified as GMFCS Levels I to III, participated in this prospective multicenter, cross-sectional study. All tools were completed by parents and participants when appropriate. Effect size indices (ESIs) for parametric variables and odds ratios for non-parametric data quantified the magnitude of differences across GMFCS levels. Binary logistic regression models determined discrimination, and receiver operating characteristic curves addressed sensitivity and specificity. Between Levels I and II, the most discriminatory tools were Gross Motor Function Measure (GMFM-66), velocity, and WeeFIM Mobility. Between Levels II and III, the most discriminatory tools were GMFM Dimension E, Pediatric Functional Independence Measure (WeeFIM) Self-Care and Mobility, cadence, and Gillette Functional Assessment Questionnaire Question 1. Large ESIs were noted for Parent and Child reports of Pediatric Outcomes Data Collection Instrument (PODCI) Sports & Physical Function, Parent report of PODCI Global Function, GMFM Dimension E, and GMFM-66 across all GMFCS level comparisons. The least discriminatory tools were the Quality of Life and cognition measures; however, these are important in comprehensive assessments of treatment effects.

Systematic approach to developing empirical interatomic potentials for III-N semiconductors

NASA Astrophysics Data System (ADS)

Ito, Tomonori; Akiyama, Toru; Nakamura, Kohji

2016-05-01

A systematic approach to the derivation of empirical interatomic potentials is developed for III-N semiconductors with the aid of ab initio calculations. The parameter values of empirical potential based on bond order potential are determined by reproducing the cohesive energy differences among 3-fold coordinated hexagonal, 4-fold coordinated zinc blende, wurtzite, and 6-fold coordinated rocksalt structures in BN, AlN, GaN, and InN. The bond order p is successfully introduced as a function of the coordination number Z in the form of p = a exp(-bZn ) if Z ≤ 4 and p = (4/Z)α if Z ≥ 4 in empirical interatomic potential. Moreover, the energy difference between wurtzite and zinc blende structures can be successfully evaluated by considering interaction beyond the second-nearest neighbors as a function of ionicity. This approach is feasible for developing empirical interatomic potentials applicable to a system consisting of poorly coordinated atoms at surfaces and interfaces including nanostructures.

Speciation analysis of inorganic arsenic by magnetic solid phase extraction on-line with inductively coupled mass spectrometry determination.

PubMed

Montoro Leal, P; Vereda Alonso, E; López Guerrero, M M; Cordero, M T Siles; Cano Pavón, J M; García de Torres, A

2018-07-01

Arsenic, one of the main environmental pollutants and potent natural poison, is a chemical element that is spread throughout the Earth's crust. It is well known that the toxicity of arsenic is highly dependent on its chemical forms. Generally, the inorganic species are more toxic than its organics forms, and As(III) is 60 times more toxic than As(V). In environmental waters, arsenic exists predominantly in two chemical forms: As(III) and As(V). In view of these facts, fast, sensitive, accurate and simple analytical methods for the speciation of inorganic arsenic in environmental waters are required. In this work, a new magnetic solid phase extraction with a hydride generation system was coupled on line with inductively coupled plasma mass spectrometry (MSPE-HG-ICP-MS). The new system was based on the retention of As(III) and As(V) in two knotted reactors filled with (Fe 3 O 4 ) magnetic nanoparticles functionalized with [1,5-bis (2-pyridyl) 3-sulfophenylmethylene] thiocarbonohydrazide (PSTH-MNPs). As(III) and total inorganic As were sequentially eluted in different reduction conditions. The concentration of As(V) was obtained by subtracting As(III) from total As. The system runs in a fully automated way and the method has proved to have a wide linear range and to be precise, sensitive and fast. The detection limits found were 2.7 and 3.2 ng/L for As(III) and total As, respectively; with relative standard deviations (RSDs) of 2.5% and 2.7% and a sample throughput of 14.4 h -1 . In order to validate the developed method, several certified reference samples of environmental waters including sea water, were analyzed and the determined values were in good agreement with the certified values. The proposed method was successfully applied to the speciation analysis of inorganic arsenic in well-water and sea water. Copyright © 2018 Elsevier B.V. All rights reserved.

Metal interferences and their removal prior to the determination of As(T) and As(III) in acid mine waters by hydride generation atomic absorption spectrometry

USGS Publications Warehouse

McCleskey, R. Blaine; Nordstrom, D. Kirk; Ball, James W.

2003-01-01

Hydride generation atomic absorption spectrometry (HGAAS) is a sensitive and selective method for the determination of total arsenic (arsenic(III) plus arsenic(V)) and arsenic(III); however, it is subject to metal interferences for acid mine waters. Sodium borohydride is used to produce arsine gas, but high metal concentrations can suppress arsine production. This report investigates interferences of sixteen metal species including aluminum, antimony(III), antimony(V), cadmium, chromium(III), chromium(IV), cobalt, copper(II), iron(III), iron(II), lead, manganese, nickel, selenium(IV), selenium(VI), and zinc ranging in concentration from 0 to 1,000 milligrams per liter and offers a method for removing interfering metal cations with cation exchange resin. The degree of interference for each metal without cation-exchange on the determination of total arsenic and arsenic(III) was evaluated by spiking synthetic samples containing arsenic(III) and arsenic(V) with the potential interfering metal. Total arsenic recoveries ranged from 92 to 102 percent for all metals tested except antimony(III) and antimony(V) which suppressed arsine formation when the antimony(III)/total arsenic molar ratio exceeded 4 or the antimony(V)/total arsenic molar ratio exceeded 2. Arsenic(III) recoveries for samples spiked with aluminum, chromium(III), cobalt, iron(II), lead, manganese, nickel, selenium(VI), and zinc ranged from 84 to 107 percent over the entire concentration range tested. Low arsenic(III) recoveries occurred when the molar ratios of metals to arsenic(III) were copper greater than 120, iron(III) greater than 70, chromium(VI) greater than 2, cadmium greater than 800, antimony(III) greater than 3, antimony(V) greater than 12, or selenium(IV) greater than 1. Low recoveries result when interfering metals compete for available sodium borohydride, causing incomplete arsine production, or when the interfering metal oxidizes arsenic(III). Separation of interfering metal cations using cation-exchange prior to hydridegeneration permits accurate arsenic(III) determinations in acid mine waters containing high concentrations of interfering metals. Stabilization of the arsenic redox species for as many as 15 months is demonstrated for samples that have been properly filtered and acidified with HCl in the field. The detection limits for the method described in this report are 0.1 micrograms per liter for total arsenic and 0.8 micrograms per liter for arsenic(III).

Parental social support, coping strategies, resilience factors, stress, anxiety and depression levels in parents of children with MPS III (Sanfilippo syndrome) or children with intellectual disabilities (ID).

PubMed

Grant, Sheena; Cross, Elaine; Wraith, James Edmond; Jones, Simon; Mahon, Louise; Lomax, Michelle; Bigger, Brian; Hare, Dougal

2013-03-01

Mucopolysaccharidosis type III (MPS III, Sanfilippo syndrome) is a lysosomal storage disorder, caused by a deficiency in one of four enzymes involved in the catabolism of the glycosaminoglycan heparan sulphate. It is a degenerative disorder, with a progressive decline in children's intellectual and physical functioning. There is currently no cure for the disorder. To date there is a paucity of research on how this disorder impacts parents psychological functioning. Specifically, research in the area has failed to employ adequate control groups to assess if the impact of this disorder on parents psychological functioning differs from parenting a child with intellectual disability (ID). The current study examined child behaviour and parental psychological functioning in 23 parents of children with MPS III and 23 parents of children with ID. Parents completed postal questionnaires about their child's behaviour and abilities and their own psychological functioning. Parents of children with MPS III reported fewer behavioural difficulties as their child aged, more severe level of intellectual disability, and similar levels of perceived social support, coping techniques, stress, anxiety and depression levels as parents of children with ID. Both groups of parents scored above the clinical cut off for anxiety and depression. Parents of children with MPS III rated themselves as significantly less future-orientated and goal directed than parents of children with ID. Services should develop support packages for parents of children with MPS III that incorporate an understanding of the unique stressors and current-difficulty approach of this population. Future research should examine gender differences between parental psychological functioning, using mixed qualitative and quantitative approaches, and utilise matched developmental level and typically developing control groups.

A solid-state hybrid density functional theory study of Prussian blue analogues and related chlorides at pressure

NASA Astrophysics Data System (ADS)

Middlemiss, Derek S.; Lawton, Lorreta M.; Wilson, Chick C.

2008-08-01

The variations with pressure in the structural, electronic and magnetic properties of a series of Prussian blue analogues (PBAs) KIMII[CrIII(CN)6] (M = VII, MnII and NiII) and associated isomorphous chlorides KIMIICrIIICl6 are investigated within a series of solid-state hybrid density functional calculations. The sensitivity of the computed properties to the choice of Hamiltonian is tested by application of functionals containing 35%, 65% and 100% admixtures of Fock exchange. Magnetic coupling constants (J) are obtained at a range of cell volumes (V), with fits of the Bloch relationship (J \\propto V^{-\\varepsilon } , ɛ typically 3-4) yielding exponents ɛ in the ranges 5.16-6.34, 8.48-12.07 and 4.00-4.51 for the antiferromagnetic (AF) VIICrIII-, ferrimagnetic (FI) MnIICrIII- and ferromagnetic (FO) NiIICrIII PBAs, respectively; and 3.33-4.99, 1.86-3.09 and 1.65-3.28 for the AF VIICrIII-, FO MnIICrIII- and FO NiIICrIII chlorides, respectively. The MnIICrIII PBA range encloses the high values ɛ~9-10 obtained in a recent joint experimental and theoretical study, and it is suggested that this strong magnetostructural effect arises due to the presence of competing AF and FO interactions in this material. Estimates of the spin ordering temperatures derived from the combination of the 35%-functional couplings with a mean field approach are in good agreement with experiment in the VIICrIII and NiIICrIII PBAs, but are too low in the MnIICrIII system. The variations with pressure in the structural parameters, charges and spin moments are also detailed, the PBA and chloride energy-volume data yielding bulk moduli in the ranges 39-53 and 36-50 GPa, respectively. Finally, the energies governing CN- ligand isomerization are estimated and successfully interpreted in terms of a simple crystal field stabilization model.

Usefulness of intraoperative electromyographic monitoring of oculomotor and abducens nerves during skull base surgery.

PubMed

Li, Zi-Yi; Li, Ming-Chu; Liang, Jian-Tao; Bao, Yu-Hai; Chen, Ge; Guo, Hong-Chuan; Ling, Feng

2017-10-01

Intraoperative neurophysiologic monitoring of the extraocular cranial nerve (EOCN) is not commonly performed because of technical difficulty and risk, reliability of the result and predictability of the postoperative function of the EOCN. We performed oculomotor nerve (CN III) and abducens nerve (CN VI) intraoperative monitoring in patients with skull base surgery by recording the spontaneous muscle activity (SMA) and compound muscle action potential (CMAP). Two types of needle electrodes of different length were percutaneously inserted into the extraocular muscles with the free-hand technique. We studied the relationships between the SMA and CMAP and postoperative function of CN III and CN VI. A total of 23 patients were included. Nineteen oculomotor nerves and 22 abducens nerves were monitored during surgery, respectively. Neurotonic discharge had a positive predictive value of less than 50% and negative predictive value of more than 80% for postoperative CN III and CN VI dysfunction. The latency of patients with postoperative CN III dysfunction was 2.79 ± 0.13 ms, longer than that with intact CN III function (1.73 ± 0.11 ms). One patient had transient CN VI dysfunction, whose CMAP latency (2.54 ms) was longer than that of intact CN VI function (2.11 ± 0.38 ms). There was no statistically significant difference between patients with paresis and with intact function. The method of intraoperative monitoring of EOCNs described here is safe and useful to record responses of SMA and CMAP. Neurotonic discharge seems to have limited value in predicting the postoperative function of CN III and CN VI. The onset latency of CMAP longer than 2.5 ms after tumor removal is probably relevant to postoperative CN III and CN VI dysfunction. However, a definite quantitative relationship has not been found between the amplitude and stimulation intensity of CMAP and the postoperative outcome of CN III and CN VI.

Control in the Rate-Determining Step Provides a Promising Strategy To Develop New Catalysts for CO2 Hydrogenation: A Local Pair Natural Orbital Coupled Cluster Theory Study.

PubMed

Mondal, Bhaskar; Neese, Frank; Ye, Shengfa

2015-08-03

The development of efficient catalysts with base metals for CO2 hydrogenation has always been a major thrust of interest. A series of experimental and theoretical work has revealed that the catalytic cycle typically involves two key steps, namely, base-promoted heterolytic H2 splitting and hydride transfer to CO2, either of which can be the rate-determining step (RDS) of the entire reaction. To explore the determining factor for the nature of RDS, we present herein a comparative mechanistic investigation on CO2 hydrogenation mediated by [M(H)(η(2)-H2)(PP3(Ph))](n+) (M = Fe(II), Ru(II), and Co(III); PP3(Ph) = tris(2-(diphenylphosphino)phenyl)phosphine) type complexes. In order to construct reliable free energy profiles, we used highly correlated wave function based ab initio methods of the coupled cluster type alongside the standard density functional theory. Our calculations demonstrate that the hydricity of the metal-hydride intermediate generated by H2 splitting dictates the nature of the RDS for the Fe(II) and Co(III) systems, while the RDS for the Ru(II) catalyst appears to be ambiguous. CO2 hydrogenation catalyzed by the Fe(II) complex that possesses moderate hydricity traverses an H2-splitting RDS, whereas the RDS for the high-hydricity Co(III) species is found to be the hydride transfer. Thus, our findings suggest that hydricity can be used as a practical guide in future catalyst design. Enhancing the electron-accepting ability of low-hydricity catalysts is likely to improve their catalytic performance, while increasing the electron-donating ability of high-hydricity complexes may speed up CO2 conversion. Moreover, we also established the active roles of base NEt3 in directing the heterolytic H2 splitting and assisting product release through the formation of an acid-base complex.

[Determination of iron(III) in Chinese herbal medicine and tea based on fluorescence quenching of 2,4-dichro-phenylfluorone].

PubMed

Dai, Gang; Aodeng, Gao-wa

2004-07-01

A new spectrofluorimetric method for the determination of trace amount of Fe(III) has been developed. This method is based on the fluorescence quenching of 2,4-dichro-phenylfluorone due to the formation of complex Fe(III)-DCIPF. In pH 5.2-5.9 buffer solution, Fe (III) and DCIPF react on each other to form a red complex. Its composition was established by method of continuous variations and molar-ratio as Fe(III): DCIPF = 1:4, the excitation and emission wavelengths were found to be 282 and 560 nm, respectively. There is a linear relationship in the range 4-24 ng x mL(-1) for Fe(III). This method is simple and rapid, and has been applied to the determination of trace iron in Chinese herbal medicine and tea samples with satisfactory results.

Assaying Benefits of Poly[styrene-4-(trimethylammonium)methyl Triiodide] in Respiratory Protection Devices

DTIC Science & Technology

2009-12-01

common laboratory mouse, Mus musculus , and treated and mechanically equivalent untreated filter media to measure infection rates as a function of...to determine viable counts. Data noise in the control experiment prevented drawing a firm conclusion but loss of viability in the aerosol phase ...protection, Triosyn U U U UU 35 Joseph Wander Reset iii TABLE OF CONTENTS Section Page 1.0 Overview

Feasibility of Using Microsoft Kinect to Assess Upper Limb Movement in Type III Spinal Muscular Atrophy Patients

PubMed Central

Siebourg-Polster, Juliane; Wolf, Detlef; Czech, Christian; Bonati, Ulrike; Fischer, Dirk; Khwaja, Omar; Strahm, Martin

2017-01-01

Although functional rating scales are being used increasingly as primary outcome measures in spinal muscular atrophy (SMA), sensitive and objective assessment of early-stage disease progression and drug efficacy remains challenging. We have developed a game based on the Microsoft Kinect sensor, specifically designed to measure active upper limb movement. An explorative study was conducted to determine the feasibility of this new tool in 18 ambulant SMA type III patients and 19 age- and gender-matched healthy controls. Upper limb movement was analysed elaborately through derived features such as elbow flexion and extension angles, arm lifting angle, velocity and acceleration. No significant differences were found in the active range of motion between ambulant SMA type III patients and controls. Hand velocity was found to be different but further validation is necessary. This study presents an important step in the process of designing and handling digital biomarkers as complementary outcome measures for clinical trials. PMID:28122039

Feasibility of Using Microsoft Kinect to Assess Upper Limb Movement in Type III Spinal Muscular Atrophy Patients.

PubMed

Chen, Xing; Siebourg-Polster, Juliane; Wolf, Detlef; Czech, Christian; Bonati, Ulrike; Fischer, Dirk; Khwaja, Omar; Strahm, Martin

2017-01-01

Although functional rating scales are being used increasingly as primary outcome measures in spinal muscular atrophy (SMA), sensitive and objective assessment of early-stage disease progression and drug efficacy remains challenging. We have developed a game based on the Microsoft Kinect sensor, specifically designed to measure active upper limb movement. An explorative study was conducted to determine the feasibility of this new tool in 18 ambulant SMA type III patients and 19 age- and gender-matched healthy controls. Upper limb movement was analysed elaborately through derived features such as elbow flexion and extension angles, arm lifting angle, velocity and acceleration. No significant differences were found in the active range of motion between ambulant SMA type III patients and controls. Hand velocity was found to be different but further validation is necessary. This study presents an important step in the process of designing and handling digital biomarkers as complementary outcome measures for clinical trials.

Structure and dynamics of the CrIII ion in aqueous solution: Ab initio QM/MM molecular dynamics simulation.

PubMed

Kritayakornupong, Chinapong; Plankensteiner, Kristof; Rode, Bernd M

2004-10-01

Structural and dynamical properties of the Cr(III) ion in aqueous solution have been investigated using a combined ab initio quantum mechanical/molecular mechanical (QM/MM) molecular dynamics simulation. The hydration structure of Cr(III) was determined in terms of radial distribution functions, coordination numbers, and angular distributions. The QM/MM simulation gives coordination numbers of 6 and 15.4 for the first and second hydration shell, respectively. The first hydration shell is kinetically very inert but by no means rigid and variations of the first hydration shell geometry lead to distinct splitting in the vibrational spectra of Cr(H(2)O)(6) (3+). A mean residence time of 22 ps was obtained for water ligands residing in the second hydration shell, which is remarkably shorter than the experimentally estimated value. The hydration energy of -1108 +/- 7 kcal/mol, obtained from the QM/MM simulation, corresponds well to the experimental hydration enthalpy value. Copyright 2004 Wiley Periodicals, Inc.

Arsenic removal by Japanese oak wood biochar in aqueous solutions and well water: Investigating arsenic fate using integrated spectroscopic and microscopic techniques.

PubMed

Niazi, Nabeel Khan; Bibi, Irshad; Shahid, Muhammad; Ok, Yong Sik; Shaheen, Sabry M; Rinklebe, Jörg; Wang, Hailong; Murtaza, Behzad; Islam, Ejazul; Farrakh Nawaz, M; Lüttge, Andreas

2018-04-15

In this study, we examined the sorption of arsenite (As(III)) and arsenate (As(V)) to Japanese oak wood-derived biochar (OW-BC) in aqueous solutions, and determined its efficiency to remove As from As-contaminated well water. Results revealed that, among the four sorption isotherm models, Langmuir model showed the best fit to describe As(III) and As(V) sorption on OW-BC, with slightly greater sorption affinity for As(V) compared to As(III) (Q L =3.89 and 3.16mgg -1 ; R 2 =0.91 and 0.85, respectively). Sorption edge experiments indicated that the maximum As removal was 81% and 84% for As(III)- and As(V)-OW-BC systems at pH7 and 6, respectively, which decreased above these pH values (76-69% and 80-58%). Surface functional groups, notably OH, COOH, CO, CH 3 , were involved in As sequestration by OW-BC, suggesting the surface complexation/precipitation and/or electrostatic interaction of As on OW-BC surface. Arsenic K-edge X-ray absorption near edge structure (XANES) spectroscopy indicated that 36% of the added As(III) was partially oxidized to As(V) in the As(III) sorption experiment, and in As(V) sorption experiment, 48% of As(V) was, albeit incompletely, reduced to As(III) on OW-BC surface. Application of OW-BC to As-contaminated well water (As: 27-144μgL -1 ; n=10) displayed that 92 to 100% of As was depleted despite in the presence of co-occurring competing anions (e.g., SO 4 2- , CO 3 2- , PO 4 3- ). This study shows that OW-BC has a great potential to remove As from solution and drinking (well) water. Overall, the combination of macroscopic sorption data and integrated spectroscopic and microscopic techniques highlight that the fate of As on biochar involves complex redox transformation and association with surface functional moieties in aquatic systems, thereby providing crucial information required for implication of biochar in environmental remediation programs. Copyright © 2017 Elsevier B.V. All rights reserved.

Acute and cumulative effects of carboplatin on renal function.

PubMed Central

Sleijfer, D. T.; Smit, E. F.; Meijer, S.; Mulder, N. H.; Postmus, P. E.

1989-01-01

Carboplatin, a cisplatinum analogue, has no reported nephrotoxicity in phase I/II studies, assessed by creatinine clearance. We prospectively determined renal function in 10 untreated lung cancer patients with normal baseline renal function, treated with carboplatin 400 mg m-2 day 1 and vincristine 2 mg day 1 and 8 every 4 weeks (max. five cycles) by means of clearance studies with 125I-sodium thalamate and 131I-hippurate to determine GFR and ERPF respectively. Tubular damage was monitored by excretion of tubular enzymes and relative beta 2-microglobulin clearance. During the first course no changes in renal function were seen. After the second course a significant fall in GFR and ERPF started, ultimately leading to a median decrease in GFR of 19.0% (range 6.8-38.7%) and in ERPF of 14% (range 0-38.9%). No increases in the excretion of tubular enzymes or changes in the relative beta 2-microglobulin clearances were seen. We conclude from our data that carboplatin causes considerable loss of renal function. Monitoring renal function in patients treated with multiple courses of carboplatin is warranted. PMID:2679841

Latent Class Analysis of Differential Item Functioning on the Peabody Picture Vocabulary Test-III

ERIC Educational Resources Information Center

Webb, Mi-young Lee; Cohen, Allan S.; Schwanenflugel, Paula J.

2008-01-01

This study investigated the use of latent class analysis for the detection of differences in item functioning on the Peabody Picture Vocabulary Test-Third Edition (PPVT-III). A two-class solution for a latent class model appeared to be defined in part by ability because Class 1 was lower in ability than Class 2 on both the PPVT-III and the…

Urinary coproporphyrin I/(I + III) ratio as a surrogate for MRP2 or other transporter activities involved in methotrexate clearance.

PubMed

Benz-de Bretagne, Isabelle; Zahr, Noël; Le Gouge, Amélie; Hulot, Jean-Sébastien; Houillier, Caroline; Hoang-Xuan, Khe; Gyan, Emmanuel; Lissandre, Séverine; Choquet, Sylvain; Le Guellec, Chantal

2014-08-01

The urinary coproporphyrin I/(I + III) ratio may be a surrogate for MRP2 activity. We conducted a prospective study in patients receiving methotrexate (MTX) to examine the relationship between this ratio and the pharmacokinetics of a MRP2 substrate. Three urine samples were collected from 81 patients for UCP I/(I + III) ratio determination: one before (P1), one at the end of MTX infusion (P2), and one on the day of hospital discharge (P3). Three polymorphisms of ABCC2 were analysed and their relationships with basal UCP I/(I + III) ratio values assessed. All associated drugs were recorded and a drug interaction score (DIS) was assigned. Population pharmacokinetic analysis was conducted to assess whether MTX clearance (MTXCL) was associated with the basal UCP I/(I + III) ratio, its variation during MTX infusion, the DIS or other common covariates. The basal UCP I/(I + III) ratio was not associated with ABCC2 polymorphisms and did not differ according to the DIS. Significant changes in the ratio were observed over time, with an increase between P1 and P2 and a decrease at P3 (P < 0.001). No association was found between basal UCP I/(I + III) ratio and MTXCL. The final model indicates that MTXCL was dependent on the change in the ratio between P1 and P3, DIS and creatinine clearance. The basal UCP I/(I + III) ratio is not predictive of MTXCL. However, it is sensitive to the presence of MTX, so it is plausible that it reflects a function modified in response to the drug. © 2014 The British Pharmacological Society.

Autecology of an arsenite chemolithotroph: sulfide constraints on function and distribution in a geothermal spring.

PubMed

D'Imperio, Seth; Lehr, Corinne R; Breary, Michele; McDermott, Timothy R

2007-11-01

Previous studies in an acid-sulfate-chloride spring in Yellowstone National Park found that microbial arsenite [As(III)] oxidation is absent in regions of the spring outflow channel where H(2)S exceeds approximately 5 microM and served as a backdrop for continued efforts in the present study. Ex situ assays with microbial mat samples demonstrated immediate As(III) oxidation activity when H(2)S was absent or at low concentrations, suggesting the presence of As(III) oxidase enzymes that could be reactivated if H(2)S is removed. Cultivation experiments initiated with mat samples taken from along the H(2)S gradient in the outflow channel resulted in the isolation of an As(III)-oxidizing chemolithotroph from the low-H(2)S region of the gradient. The isolate was phylogenetically related to Acidicaldus and was characterized in vitro for spring-relevant properties, which were then compared to its distribution pattern in the spring as determined by denaturing gradient gel electrophoresis and quantitative PCR. While neither temperature nor oxygen requirements appeared to be related to the occurrence of this organism within the outflow channel, H(2)S concentration appeared to be an important constraint. This was verified by in vitro pure-culture modeling and kinetic experiments, which suggested that H(2)S inhibition of As(III) oxidation is uncompetitive in nature. In summary, the studies reported herein illustrate that H(2)S is a potent inhibitor of As(III) oxidation and will influence the niche opportunities and population distribution of As(III) chemolithotrophs.

Autecology of an Arsenite Chemolithotroph: Sulfide Constraints on Function and Distribution in a Geothermal Spring▿

PubMed Central

D'Imperio, Seth; Lehr, Corinne R.; Breary, Michele; McDermott, Timothy R.

2007-01-01

Previous studies in an acid-sulfate-chloride spring in Yellowstone National Park found that microbial arsenite [As(III)] oxidation is absent in regions of the spring outflow channel where H2S exceeds ∼5 μM and served as a backdrop for continued efforts in the present study. Ex situ assays with microbial mat samples demonstrated immediate As(III) oxidation activity when H2S was absent or at low concentrations, suggesting the presence of As(III) oxidase enzymes that could be reactivated if H2S is removed. Cultivation experiments initiated with mat samples taken from along the H2S gradient in the outflow channel resulted in the isolation of an As(III)-oxidizing chemolithotroph from the low-H2S region of the gradient. The isolate was phylogenetically related to Acidicaldus and was characterized in vitro for spring-relevant properties, which were then compared to its distribution pattern in the spring as determined by denaturing gradient gel electrophoresis and quantitative PCR. While neither temperature nor oxygen requirements appeared to be related to the occurrence of this organism within the outflow channel, H2S concentration appeared to be an important constraint. This was verified by in vitro pure-culture modeling and kinetic experiments, which suggested that H2S inhibition of As(III) oxidation is uncompetitive in nature. In summary, the studies reported herein illustrate that H2S is a potent inhibitor of As(III) oxidation and will influence the niche opportunities and population distribution of As(III) chemolithotrophs. PMID:17827309

Cysteine-Functionalized Chitosan Magnetic Nano-Based Particles for the Recovery of Light and Heavy Rare Earth Metals: Uptake Kinetics and Sorption Isotherms

PubMed Central

Galhoum, Ahmed A.; Mafhouz, Mohammad G.; Abdel-Rehem, Sayed T.; Gomaa, Nabawia A.; Atia, Asem A.; Vincent, Thierry; Guibal, Eric

2015-01-01

Cysteine-functionalized chitosan magnetic nano-based particles were synthesized for the sorption of light and heavy rare earth (RE) metal ions (La(III), Nd(III) and Yb(III)). The structural, surface, and magnetic properties of nano-sized sorbent were investigated by elemental analysis, FTIR, XRD, TEM and VSM (vibrating sample magnetometry). Experimental data show that the pseudo second-order rate equation fits the kinetic profiles well, while sorption isotherms are described by the Langmuir model. Thermodynamic constants (ΔG°, ΔH°) demonstrate the spontaneous and endothermic nature of sorption. Yb(III) (heavy RE) was selectively sorbed while light RE metal ions La(III) and Nd(III) were concentrated/enriched in the solution. Cationic species RE(III) in aqueous solution can be adsorbed by the combination of chelating and anion-exchange mechanisms. The sorbent can be efficiently regenerated using acidified thiourea. PMID:28347004

TMJ in facial class III deformity. Condylar morphology relations

PubMed Central

Muñoz, Gonzalo; Olate, Sergio; Cantín, Mario; Vásquez, Bélgica; del Sol, Mariano

2014-01-01

Class III dentofacial deformities (DF-III) are classified as a severe functional and esthetic anomaly. This work aims to describe the condylar morphology of subjects with DF-III and indication of correction through orthognatic surgery. A descriptive study was designed in the Division of Oral and Maxillofacial Surgery of the Universidad de La Frontera, Chile, where 14 patients were examined with conventional cephalometric studies to determine the surgical indication; then, cone beam CT images were recorded for the morphometric analyses on the coronal and axial slices, considering linear measurements in the middle, basal and anteroposterior areas. The data were analyzed with the student’s t-test, considering p < 0.05 statistically significant. The results revealed condylar size differences of less than 1 mm between the left and right condyles, considering average widths of 17.03 mm in the right condyle and 17.86 mm in the left condyle. Vertically, the observed averages were 17.17 mm in the right condyle and 17.04 mm in the left condyle; no statistical differences were observed. It can be concluded that there are no differences in the measurements when the two condyles are compared in this type of subject. PMID:25356190

Application of granular activated carbon/MnFe2O4 composite immobilized on C. glutamicum MTCC 2745 to remove As(III) and As(V): Kinetic, mechanistic and thermodynamic studies

NASA Astrophysics Data System (ADS)

Podder, M. S.; Majumder, C. B.

2016-01-01

The main objective of the present study was to investigate the efficiency of Corynebacterium glutamicum MTCC 2745 immobilized on granular activated carbon/MnFe2O4 (GAC/MnFe2O4) composite to treat high concentration of arsenic bearing wastewater. Non-linear regression analysis was done for determining the best-fit kinetic model on the basis of three correlation coefficients and three error functions and also for predicting the parameters involved in kinetic models. The results showed that Fractal-like mixed 1,2 order model for As(III) and Brouser-Weron-Sototlongo as well as Fractal-like pseudo second order models for As(V) were proficient to provide realistic description of biosorption/bioaccumulation kinetic. Applicability of mechanistic models in the current study exhibited that the rate governing step in biosorption/bioaccumulation of both As(III) and As(V) was film diffusion rather than intraparticle diffusion. The evaluated thermodynamic parameters ΔG0, ΔH0 and ΔS0 revealed that biosorption/bioaccumulation of both As(III) and As(V) was feasible, spontaneous and exothermic under studied conditions.

A color-tunable luminescent material with functionalized graphitic carbon nitride as multifunctional supports

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Jiutian; Cao, Yudong; Fan, Hai

2015-12-15

A color-tunable luminescent material was prepared based on the composition of functionalized graphitic carbon nitride (g-C{sub 3}N{sub 4}) and europium (III). The functionalized g-C{sub 3}N{sub 4} layers not only behave as multifunctional supports including ligand coordinated with europium (III) and a support structure for the formation of the luminescent material, but exhibit excitation wavelength-dependent luminescence, thus the energy transfer between the functionalized g-C{sub 3}N{sub 4} and europium (III) can match very well by controlling the emission wavelength of functionalized g-C{sub 3}N{sub 4}. The as-prepared materials was comprehensively characterized via X-ray photoelectron spectroscopy, Fourier Transform Infrared spectroscopy, X-ray scattering techniques, Ultravioletmore » and Visible spectrophotometer, fluorescence spectrophotometer, thermogravimetric analysis, etc. The luminescent material exhibits multi-color emissions which are consistent with the characteristic emissions of europium (III) and functionalized g-C{sub 3}N{sub 4}, and the photoluminescence quality and density of the europium (III) can be greatly enhanced. The brilliant optical properties of the materials make them suiting for multipurpose applications in practical fields. - Graphical abstract: Schematic illustration of the synthesis and basic composition of the luminescent material. Inset figures were luminescence emission spectra of g-C{sub 3}N{sub 4} (A), europium (III) complex (a) and luminescent material (b) with the same concentration in (B) (K{sub ex}=350 nm) and photographs of (left) H{sub 2}O and (right) the H{sub 2}O dispersion of luminescence emission spectra under 350 nm UV radiation. The energy transfer in the luminescent material matchs very well and it exhibits multi-color emissions simultaneously. The enhanced photoluminescence quality and density of the europium (III) makes them suiting for multipurpose applications in practical fields. - Highlights: • Luminescent material exhibits multi-color emissions when excited by single wavelength. • The energy trsnsfer between functionalized g-C{sub 3}N{sub 4} and europium matches very vell. • Functionalized g-C{sub 3}N{sub 4} exhibits excitation wavelength-depengdent bright blue luminescence. • Functionalized g-C{sub 3}N{sub 4} layer provided as multifunctional supports.« less

Preconcentration of trace lead and iron on activated carbon functionalized by o-Anisic acid derivatives prior to their determination in environmental samples.

PubMed

Tian, Hua; Hu, Zheng; He, Qun; Liu, Xueliang; Zhang, Li; Chang, Xijun

2012-07-01

Two solid-phase adsorbents (phase I and phase II) were synthesized successfully that o-Anisic acid derivatives were evenly functionalized on the surface of activated carbon. It was certified that the two adsorbents were applied to preconcentrate and separate trace levels of Pb(II) and Fe(III) from natural liquid samples with satisfactory results. It can be found that the adsorption capacity of the ions adsorbed on phase I and phase II was 48.3 and 85.7 mg g(-1) for Pb(II), 39.5 and 72.5 mg g(-1) for Fe(III), respectively. The detection limit (3σ) of the method separated on phase I and phase II was 0.12 and 0.09 ng mL(-1) for Pb(II), 0.23 and 0.17 ng mL(-1) for Fe(III), respectively. The relative standard deviation (R.S.D.) of the method was lower than 3.0%. The adsorption and desorption property of two kinds of adsorbents was comparatively studied, respectively. The adsorption selectivity of heavy metal ions at certain pH, the adsorption kinetics, the condition of complete elution, the effect of coexisting ions, the adsorption capacity and adsorption isotherm modes were examined. Based on the experimental datum determined by inductively coupled plasma optical emission spectrometry (ICP-OES), it was certified that the adsorption on the surface of adsorbents was in strict accordance with the monolayer adsorption principle. The structural features of series of multidentate ligand modified on adsorption matrix had been obtained. These conclusions can provide reference for synthesizing an efficient adsorbent which is specific to remove a particular kind of contaminant. Copyright © 2012 Elsevier B.V. All rights reserved.

βIII-Gal is involved in galactan reduction during phloem element differentiation in chickpea stems.

PubMed

Martín, Ignacio; Hernández-Nistal, Josefina; Albornos, Lucía; Labrador, Emilia; Dopico, Berta

2013-06-01

βIII-Gal, a member of the chickpea β-galactosidase family, is the enzyme responsible for the cell wall autolytic process. This enzyme, whose activity increases during epicotyl growth, displays significant hydrolytic activity against cell wall pectins, and its natural substrate has been determined as an arabinogalactan from the pectic fraction of the cell wall. In the present work, the localization of βIII-Gal in different seedling and plant organs was analyzed by using specific anti-βIII-Gal antibodies. Our results revealed that besides its possible role in cell wall loosening and in early events during primary xylem and phloem fiber differentiation βIII-Gal acts on the development of sieve elements. Localization of the enzyme in this tissue, both in epicotyls and radicles from seedlings and in the different stem internodes, is consistent with the reduction in galactan during the maturation of phloem elements, as can be observed with LM5 antibodies. Thus, βIII-Gal could act on its natural substrate, the neutral side chains of rhamnogalacturonan I, contributing to cell wall reinforcement allowing phloem elements to differentiate, and conferring the necessary strengthening of the cell wall to fulfill its function. This work completes the immunolocation studies of all known chickpea β-galactosidases. Taken together, our results reflect the broad range of developmental processes covered by different members of this protein family, and confirm their crucial role in cell wall remodeling during tissue differentiation.

Complexation and molecular modeling studies of europium(III)-gallic acid-amino acid complexes.

PubMed

Taha, Mohamed; Khan, Imran; Coutinho, João A P

2016-04-01

With many metal-based drugs extensively used today in the treatment of cancer, attention has focused on the development of new coordination compounds with antitumor activity with europium(III) complexes recently introduced as novel anticancer drugs. The aim of this work is to design new Eu(III) complexes with gallic acid, an antioxida'nt phenolic compound. Gallic acid was chosen because it shows anticancer activity without harming health cells. As antioxidant, it helps to protect human cells against oxidative damage that implicated in DNA damage, cancer, and accelerated cell aging. In this work, the formation of binary and ternary complexes of Eu(III) with gallic acid, primary ligand, and amino acids alanine, leucine, isoleucine, and tryptophan was studied by glass electrode potentiometry in aqueous solution containing 0.1M NaNO3 at (298.2 ± 0.1) K. Their overall stability constants were evaluated and the concentration distributions of the complex species in solution were calculated. The protonation constants of gallic acid and amino acids were also determined at our experimental conditions and compared with those predicted by using conductor-like screening model for realistic solvation (COSMO-RS) model. The geometries of Eu(III)-gallic acid complexes were characterized by the density functional theory (DFT). The spectroscopic UV-visible and photoluminescence measurements are carried out to confirm the formation of Eu(III)-gallic acid complexes in aqueous solutions. Copyright © 2016 Elsevier Inc. All rights reserved.

Chitosan-bound pyridinedicarboxylate Ni(II) and Fe(III) complex biopolymer films as waste water decyanidation agents.

PubMed

Adewuyi, Sheriff; Jacob, Julianah Modupe; Olaleye, Oluwatoyin Omolola; Abdulraheem, Taofiq Olanrewaju; Tayo, Jubril Ayopo; Oladoyinbo, Fatai Oladipupo

2016-10-20

Chitosan is a biopolymer with immense structural advantage for chemical and mechanical modifications to generate novel properties, functions and applications. This work depicts new pyridinedicarboxylicacid (PDC) crosslinked chitosan-metal ion films as veritable material for cyanide ion removal from aqueous solution. The PDC-crosslinked chitosan-metal films (PDC-Chit-Ni(II) and PDC-Chit-Fe(III)) were formed by complexing PDC-crosslinked chitosan film with anhydrous nickel(II) and iron(III) chloride salts respectively. The PDC-Chit and its metal films were characterized employing various analytical and spectroscopic techniques. The FT-IR, UV-vis and the XRD results confirm the presence of the metal ions in the metal coordinated PDC-crosslinked chitosan film. The surface morphological difference of PDC-Chit-Ni(II) film before and after decyanidation was explored with scanning electron microscopy. Furthermore, the quantitative amount of nickel(II) and iron(III) present in the complex were determined using Atomic Absorption Spectrophotometer as 32.3 and 37.2μg/g respectively which portends the biopolymer film as a good complexing agent. Removal of cyanide from aqueous solution with PDC-Chit, PDC-Chit-Ni(II) and PDC-Chit-Fe(III) films was studied with batch equilibrium experiments. At equilibrium, decyanidation capacity (DC) followed the order PDC-Chit-Ni (II)≈PDC-Chit-Fe(III)>PDC-Chit. PDC-Chit-Ni(II) film gave 100% CN(-) removal within 40min decyanidation owing to favorable coordination geometry. Copyright © 2016 Elsevier Ltd. All rights reserved.

Stress evolution of GaN/AlN heterostructure grown on 6H-SiC substrate by plasma assisted molecular beam epitaxy

NASA Astrophysics Data System (ADS)

Agrawal, M.; Ravikiran, L.; Dharmarasu, N.; Radhakrishnan, K.; Karthikeyan, G. S.; Zheng, Y.

2017-01-01

The stress evolution of GaN/AlN heterostructure grown on 6H-SiC substrate by plasma assisted molecular beam epitaxy (PA-MBE) has been studied. AlN nucleation layer and GaN layer were grown as a function of III/V ratio. GaN/AlN structure is found to form buried cracks when AlN is grown in the intermediate growth regime(III/V˜1)and GaN is grown under N-rich growth regime (III/V<1). The III/V ratio determines the growth mode of the layers that influences the lattice mismatch at the GaN/AlN interface. The lattice mismatch induced interfacial stress at the GaN/AlN interface relaxes by the formation of buried cracks in the structure. Additionally, the stress also relaxes by misorienting the AlN resulting in two misorientations with different tilts. Crack-free layers were obtained when AlN and GaN were grown in the N-rich growth regime (III/V<1) and metal rich growth regime (III/V≥1), respectively. AlGaN/GaN high electron mobility transistor (HEMT) heterostructure was demonstrated on 2-inch SiC that showed good two dimensional electron gas (2DEG) properties with a sheet resistance of 480 Ω/sq, mobility of 1280 cm2/V.s and sheet carrier density of 1×1013 cm-2.

Accurate critical pressures for structural phase transitions of group IV, III-V, and II-VI compounds from the SCAN density functional

NASA Astrophysics Data System (ADS)

Shahi, Chandra; Sun, Jianwei; Perdew, John P.

2018-03-01

Most of the group IV, III-V, and II-VI compounds crystallize in semiconductor structures under ambient conditions. Upon application of pressure, they undergo structural phase transitions to more closely packed structures, sometimes metallic phases. We have performed density functional calculations using projector augmented wave (PAW) pseudopotentials to determine the transition pressures for these transitions within the local density approximation (LDA), the Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA), and the strongly constrained and appropriately normed (SCAN) meta-GGA. LDA underestimates the transition pressure for most of the studied materials. PBE under- or overestimates in many cases. SCAN typically corrects the errors of LDA and PBE for the transition pressure. The accuracy of SCAN is comparable to that of computationally expensive methods like the hybrid functional HSE06, the random phase approximation (RPA), and quantum Monte Carlo (QMC), in cases where calculations with these methods have been reported, but at a more modest computational cost. The improvement from LDA to PBE to SCAN is especially clearcut and dramatic for covalent semiconductor-metal transitions, as for Si and Ge, where it reflects the increasing relative stabilization of the covalent semiconducting phases under increasing functional sophistication.

Fate of combat nerve injury.

PubMed

Beltran, Michael J; Burns, Travis C; Eckel, Tobin T; Potter, Benjamin K; Wenke, Joseph C; Hsu, Joseph R

2012-11-01

Assess a cohort of combat-related type III open tibia fractures with peripheral nerve injury to determine the injury mechanism and likelihood for recovery or improvement in nerve function. Retrospective study. Three military medical centers. Out of a study cohort of 213 type III open tibia fractures, 32 fractures (in 32 patients) with a total of 43 peripheral nerve injuries (peroneal or tibial) distal to the popliteal fossa met inclusion criteria and were available for follow-up at an average of 20 months (range, 2-48 months). Clinical assessment of motor and sensory nerve improvement. There was a 22% incidence of peripheral nerve injury in the study cohort. At an average follow-up of 20 months (range, 2-48 months), 89% of injured motor nerves were functional, whereas the injured sensory nerves had function in 93%. Fifty percent and 27% of motor and sensory injuries demonstrated improvement, respectively (P = 0.043). With the numbers available, there was no difference in motor or sensory improvement based on mechanism of injury, fracture severity or location, soft tissue injury, or specific nerve injured. In the subset of patients with an initially impaired sensory examination, full improvement was related to fracture location (P = 0.0164). Type III open tibia fractures sustained in combat are associated with a 22% incidence of peripheral nerve injury, and the majority are due to multiple projectile penetrating injury. Despite the severe nature of these injuries, the vast majority of patients had a functional nerve status by an average of 2-year follow-up. Based on these findings, discussions regarding limb salvage and amputation should not be overly influenced by the patient's peripheral nerve status. Prognostic Level II. See Instructions for Authors for a complete description of levels of evidence.

The endothelin pathway: a protective or detrimental target of bardoxolone methyl on cardiac function in patients with advanced chronic kidney disease?

PubMed

Camer, Danielle; Huang, Xu-Feng

2014-01-01

Bardoxolone methyl has been reported to cause detrimental cardiovascular events in the terminated BEACON Phase III human clinical trial via modulation of the renal endothelin pathway. However, the effects of bardoxolone methyl administration on the endothelin pathway in the heart are unknown. Our purpose in this perspective is to highlight the distinctive opposing roles of the renal and heart endothelin pathway in cardiac function. Furthermore, we address the need for further investigation in order to determine if bardoxolone methyl has a protective role in cardiac function through the suppression of the endothelin pathway in the heart. © 2014 S. Karger AG, Basel.

Analysis of the HIV-1 LTR NF-kappaB-proximal Sp site III: evidence for cell type-specific gene regulation and viral replication.

PubMed

McAllister, J J; Phillips, D; Millhouse, S; Conner, J; Hogan, T; Ross, H L; Wigdahl, B

2000-09-01

It has been widely demonstrated that the human immunodeficiency virus type 1 (HIV-1) envelope, specifically the V3 loop of the gp120 spike, evolves to facilitate adaptation to different cellular populations within an infected host. Less energy has been directed at determining whether the viral promoter, designated the long terminal repeat (LTR), also exhibits this adaptive quality. Because of the unique nature of the cell populations infected during the course of HIV-1 infection, one might expect the opportunity for such adaptation to exist. This would permit select viral species to take advantage of the different array of conditions and factors influencing transcription within a given cell type. To investigate this hypothesis, the function of natural variants of the NF-kappaB-proximal Sp element (Sp site III) was examined in human cell line models of the two major cell types infected during the natural course of HIV-1 infection, T cells and monocytes. Utilizing the HIV-1 LAI molecular clone, which naturally contains a high-affinity Sp site III, substitution of low-affinity Sp sites in place of the natural site III element markedly decreased viral replication in Jurkat T cells. However, these substitutions had relatively small effects on viral replication in U-937 monocytic cells. Transient transfections of HIV-1 LAI-based LTR-luciferase constructs into these cell lines suggest that the large reduction in viral replication in Jurkat T cells, caused by low-affinity Sp site III variants, may result from reduced basal as well as Vpr- and Tat-activated LTR activities in Jurkat T cells compared to those in U-937 monocytic cells. When the function of Sp site III was examined in the context of HIV-1 YU-2-based LTR-luciferase constructs, substitution of a high-affinity element in place of the natural low-affinity element resulted in increased basal YU-2 LTR activity in Jurkat T cells and reduced activity in U-937 monocytic cells. These observations suggest that recruitment of Sp family members to Sp site III is of greater importance to the function of the viral promoter in the Jurkat T cell line as compared to the U-937 monocytic cell line. These observations also suggest that other regions of the LTR may compensate for Sp recruitment defects in specific cell populations. Copyright 2000 Academic Press.

Influencing factors of NT-proBNP level inheart failure patients with different cardiacfunctions and correlation with prognosis.

PubMed

Xu, Liang; Chen, Yanchun; Ji, Yanni; Yang, Song

2018-06-01

Factors influencing N-terminal pro-brain natriuretic peptide (NT-proBNP) level in heart failure patients with different cardiac functions were identified to explore the correlations with prognosis. Eighty heart failure patients with different cardiac functions treated in Yixing People's Hospital from January 2016 to June 2017 were selected, and divided into two groups (group with cardiac function in class II and below and group with cardiac function in class III and above), according to the cardiac function classification established by New York Heart Association (NYHA). Blood biochemical test and outcome analysis were conducted to measure serum NT-proBNP and matrix metalloproteinase-9 (MMP-9) levels in patients with different cardiac functions, and correlations between levels of NT-proBNP and MMP-9 and left ventricular ejection fraction (LVEF) level were analyzed in patients with different cardiac functions at the same time. In addition, risk factors for heart failure in patients with different cardiac functions were analyzed. Compared with the group with cardiac function in class III and above, the group with cardiac function in class II and below had significantly lower serum NT-proBNP and MMP-9 levels (p<0.05). For echocardiogram indexes, left ventricular end-diastolic diameter (LVEDD) and left ventricular end-systolic diameter (LVESD) in the group with cardiac function in class II and below were obviously lower than those in the group with cardiac function in class III and above (p<0.05), while LVEF was higher in group with cardiac function in class II and below than that in group with cardiac function in class III and above (p<0.05). NT-proBNP and MMP-9 levels were negatively correlated with LVEF level [r=-0.8517 and -0.8517, respectively, p<0.001 (<0.05)]. Cardiac function in class III and above, increased NT-proBNP, increased MMP-9 and decreased LVEF were relevant risk factors and independent risk factors for heart failure in patients with different cardiac functions. NT-proBNP and MMP-9 levels are negatively correlated with LVEF in patients regardless of the cardiac function class. Therefore, attention should be paid to patients who have cardiac function in class III and above, increased NT-proBNP and MMP-9 levels and decreased LVEF in clinical practices, so as to actively prevent and treat heart failure.

Exchange coupling and magnetic anisotropy in a family of bipyrimidyl radical-bridged dilanthanide complexes: density functional theory and ab initio calculations.

PubMed

Zhang, Yi-Quan; Luo, Cheng-Lin; Zhang, Qiang

2014-05-05

The origin of the magnetic anisotropy energy barriers in a series of bpym(-) (bpym = 2,2'-bipyrimidine) radical-bridged dilanthanide complexes [(Cp*2Ln)2(μ-bpym)](+) [Cp* = pentamethylcyclopentadienyl; Ln = Gd(III) (1), Tb(III) (2), Dy(III) (3), Ho(III) (4), Er(III) (5)] has been explored using density functional theory (DFT) and ab initio methods. DFT calculations show that the exchange coupling between the two lanthanide ions for each complex is very weak, but the antiferromagnetic Ln-bpym(-) couplings are strong. Ab initio calculations show that the effective energy barrier of 2 or 3 mainly comes from the contribution of a single Tb(III) or Dy(III) fragment, which is only about one third of a single Ln energy barrier. For 4 or 5, however, both of the two Ho(III) or Er(III) fragments contribute to the total energy barrier. Thus, it is insufficient to only increase the magnetic anisotropy energy barrier of a single Ln ion, while enhancing the Ln-bpym(-) couplings is also very important. Copyright © 2014 Wiley Periodicals, Inc.

Online spectrophotometric determination of Fe(II) and Fe(III) by flow injection combined with low pressure ion chromatography

NASA Astrophysics Data System (ADS)

Chen, Shujuan; Li, Nan; Zhang, Xinshen; Yang, Dongjing; Jiang, Heimei

2015-03-01

A simple and new low pressure ion chromatography combined with flow injection spectrophotometric procedure for determining Fe(II) and Fe(III) was established. It is based on the selective adsorption of low pressure ion chromatography column to Fe(II) and Fe(III), the online reduction reaction of Fe(III) and the reaction of Fe(II) in sodium acetate with phenanthroline, resulting in an intense orange complex with a suitable absorption at 515 nm. Various chemical (such as the concentration of colour reagent, eluant and reductive agent) and instrumental parameters (reaction coil length, reductive coil length and wavelength) were studied and were optimized. Under the optimum conditions calibration graph of Fe(II)/Fe(III) was linear in the Fe(II)/Fe(III) range of 0.040-1.0 mg/L. The detection limit of Fe(III) and Fe(II) was respectively 3.09 and 1.55 μg/L, the relative standard deviation (n = 10) of Fe(II) and Fe(III) 1.89% and 1.90% for 0.5 mg/L of Fe(II) and Fe(III) respectively. About 2.5 samples in 1 h can be analyzed. The interfering effects of various chemical species were studied. The method was successfully applied in the determination of water samples.

Neuropsychological dysfunction, mood disturbance, and emotional status of munitions workers.

PubMed

Bowler, R M; Lezak, M; Booty, A; Hartney, C; Mergler, D; Levin, J; Zisman, F

2001-01-01

The objective of this study was to compare the neuropsychological function, emotional status, visual function, and illness prevalence of 265 former munitions plant workers (M age = 56.7 years, M years of education = 12.07; 201 African American, 64 White) exposed to organic solvents for an average of 17.03 years with that of a group of 77 unexposed controls (M age = 51.3 years, M years of education = 13.07; 30 African American, 47 White). Neuropsychological tests were selected from the World Health Organization Neurobehavioral Core Test Battery, Wechsler Adult Intelligence Scale-III (WAIS-III), and Wechsler Memory Scale-III (WMS-III) and also included the Brief Symptom Inventory, Profile of Mood States, Beck Anxiety Inventory, and Beck Depression Inventory. Vision tests included the Lanthony d-15 color vision, the Vistech Contrast Sensitivity, and the Snellen. The exposed group showed greater deficits than the controls in verbal learning (WMS-III Logical Memory I Learning Slope and Word Lists I Recall), visuomotor tracking speed (Cancellation H, WAIS-III Digit Symbol-Coding) and psychomotor function (Dynamometer and Grooved Pegboard), and dysfunction in emotional status, illness prevalence, and visual function. African American workers reported higher levels of exposure than Whites. Exposure relations demonstrated increased neuropsychological dysfunction with increased exposure.

[Rome III classification of functional gastrointestinal disorders in children with chronic abdominal pain].

PubMed

Plocek, Anna; Wasowska-Królikowska, Krystyna; Toporowska-Kowalska, Ewa

2010-01-01

The updated Rome III Classification of paediatric functional gastrointestinal disorders (FGIDs) associated with abdominal pain comprises: functional dyspepsia (FD), irritable bowel syndrome (IBS), abdominal migraine, functional abdominal pain (FAP), functional abdominal pain syndrome (FAPS). To assess the value of the Rome criteria in identifying FGIDs in children with chronic abdominal pain. The study group consisted of 439 consecutive paediatric patients (192 boys and 247 girls) aged 4-18 years (mean age was 11.95 +/- 3.89 years) referred to the Paediatric Gastroenterology Department at Medical University of Lodz from January 2008 to June 2009 for evaluation of abdominal pain of at least 2 months' duration. After exclusion of organic disease children suspected of functional chronic abdominal pain were categorized with the use of Rome III criteria of FGIDs associated with abdominal pain (H2a-H2d1) and the Questionnaire on Paediatric Gastrointestinal Symptoms (with the permission of doctor L. S. Walker). The patients with known nonabdominal organic disease, chronic illness or handicap were excluded. In 161 patients (36.58%) organic etiology was confirmed. Of the 278 children (63.42%) with functional chronic abdominal pain, 228 (82.02%) met the Rome III criteria for FGIDs associated with abdominal pain (FD, 15.5%; IBS, 21.6%; abdominal migraine, 5%; FAP 24.5%; FAPS, 15.9%). Fifty cases (17.98%) did not fulfill the criteria for subtypes of abdominal pain-related FGIDs--mainly due to different as defined by Rome III criteria (at least once per week) frequency of symptom presentation. (1) In the authors'investigations FGIDs was the most frequent cause of chronic abdominal pain in children. (2) The significant number of children with nonclassified FGIDs implies the need to modify the diagnostic criteria of Rome III classification concerning the prevalence of symptoms.

Validation of the Rome III criteria and alarm symptoms for recurrent abdominal pain in children.

PubMed

Gijsbers, Carolien F M; Benninga, Marc A; Schweizer, Joachim J; Kneepkens, C M Frank; Vergouwe, Yvonne; Büller, Hans A

2014-06-01

Rome criteria were formulated to define functional gastrointestinal disorders (Rome III criteria, 2006) excluding organic diagnoses when alarm symptoms were absent. The aims of the study were to validate the Rome III criteria as to their capacity to differentiate between organic and functional abdominal pain and to assess the role of alarm symptoms in this differentiation. During 2 years all of the patients (ages 4-16 years) presenting with recurrent abdominal pain (Apley criteria) and referred to secondary care were included. Clinical diagnoses were based on protocolized evaluation and intervention with 6-month follow-up. Alarm symptoms were registered. Rome III criteria for functional pain syndromes were assigned independently. Descriptive statistical analyses were performed. In 200 patients (87 boys, mean age 8.8 years), organic (17%), functional (40%), combined organic and functional (9%), spontaneous recovery (27%), and other (8%) clinical diagnoses were established. Alarm symptoms were found in 57.5% (organic causes 56%, functional causes 61%). The evaluation for Rome symptom clusters revealed symptoms of irritable bowel syndrome in 27%, functional dyspepsia in 15%, functional abdominal pain in 28%, functional abdominal pain syndrome in 14.5%, and no pain syndrome in 15.5%. Rome diagnoses, based on symptoms and absence of alarm symptoms, predicted functional clinical diagnosis with sensitivity 0.35 (95% confidence interval 0.27-0.43), specificity 0.60 (0.46-0.73), positive predictive value 0.71 (0.61-0.82), and negative predictive value of 0.24 (0.17-0.32). The Rome III criteria for abdominal pain are not specific enough to rule out organic causes. Alarm symptoms do not differentiate between organic and functional abdominal pain.

Determination of Grayanotoxins from Rhododendron brachycarpum in Dietary Supplements and Homemade Wine by Liquid Chromatography-Quadrupole Time-of-Flight-Mass Spectrometry and Liquid Chromatography-Tandem Mass Spectrometry.

PubMed

Hwang, Taeik; Noh, Eunyoung; Jeong, Ji Hye; Park, Sung-Kwan; Shin, Dongwoo; Kang, Hoil

2018-02-28

A sensitive and specific high-performance liquid chromatography-quadrupole time-of-flight-mass spectrometry (LC-QTOF-MS) method combined with liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed for the determination of grayanotoxins I and III in dietary supplements and homemade wine. Grayanotoxins I and III were successfully extracted using solid-phase extraction cartridges, characterized by LC-QTOF-MS, and quantitated by LC-MS/MS. The LC-MS/MS calibration curves were linear over concentrations of 10-100 ng/mL (grayanotoxin I) and 20-400 ng/mL (grayanotoxin III). Grayanotoxins I and III were found in 51 foodstuffs, with quantitative determinations revealing total toxin concentrations of 18.4-101 000 ng/mL (grayanotoxin I) and 15.3-56 000 ng/mL (grayanotoxin III). The potential of the validated method was demonstrated by successful quantitative analysis of grayanotoxins I and III in dietary supplements and homemade wine; the method appears suitable for the routine detection of grayanotoxins I and III from Rhododendron brachycarpum.

New Generation Strategic Submarine Study

DTIC Science & Technology

1977-01-01

Ship Propulsion System . 111-22 III- A -6 Simplified Functional Diagram - Steam-Feed Flow System . 111-23 III- A -7...16 Aa Tabte XIZ- A -3 System (Element) Functional Analysis ResuZts--Engineering p Plant Subsystem SYSTEM (ELEMENT) FUNCTION Ll A . Ship Propulsion 1...FUNCTION A . Ship Propulsion (cont’d) 9. SSTG Throttle Valves * Provide frequency control of the ship’s service turbine generators, startup and

Selective speciation and determination of inorganic arsenic in water, food and biological samples.

PubMed

Tuzen, Mustafa; Saygi, Kadriye Ozlem; Karaman, Isa; Soylak, Mustafa

2010-01-01

A procedure for the speciation of arsenic(III) and arsenic(V) in natural water samples has been established in the presented work. Arsenic(III) ions were quantitatively recovered on Alternaria solani coated Diaion HP-2MG resin at pH 7, while the recoveries of arsenic(V) was below 10%. Arsenic(V) in the mixing solution containing As(III) and As(V) was reduced by using KI and L(+) ascorbic acid solution, then the procedure was applied to determination of total arsenic. Arsenic(V) was calculated as the difference between the total arsenic content and As(III) content. The determination of arsenic was performed by using hydride generation atomic absorption spectrometry. The influences of some alkali, earth alkali and transition metals on the biosorption of arsenic(III) were investigated. The preconcentration factor was 35. The detection limits for As(III) (N=20, k=3) was found as 11 ng L(-1). The relative standard deviation and relative error of the determinations were found to be lower than 7% and 4%, respectively. The accuracy of the method was confirmed with certified reference materials. The method was successively applied for the determination and speciation of inorganic arsenic in water, food and biological samples. Copyright 2009 Elsevier Ltd. All rights reserved.

The numerical and functional responses of a granivorous rodent and the fate of Neotropical tree seeds

USGS Publications Warehouse

Klinger, R.; Rejmanek, M.

2009-01-01

Despite their potential to provide mechanistic explanations of rates of seed dispersal and seed fate, the functional and numerical responses of seed predators have never been explicitly examined within this context. Therefore, we investigated the numerical response of a small-mammal seed predator, Heteromys desmarestianus, to disturbance-induced changes in food availability and evaluated the degree to which removal and fate of seeds of eight tree species in a lowland tropical forest in Belize were related to the functional response of H. desmarestianus to varying seed densities. Mark-recapture trapping was used to estimate abundance of H. desmarestianus in six 0.5-ha grids from July 2000 to September 2002. Fruit availability and seed fate were estimated in each grid, and two experiments nested within the grids were used to determine (1) the form of the functional response for nine levels of fruit density (2-32 fruits/m 2), (2) the removal rate and handling times, and (3) the total proportion of fruits removed. The total proportion of fruits removed was determined primarily by the numerical response of H. desmarestianus to fruit availability, while removal rates and the proportion of seeds eaten or cached were related primarily to the form of the functional response. However, the numerical and functional responses interacted; H. desmarestianus showed strong spatial and temporal numerical responses to total fruit availability, and their density relative to fruit availability resulted in variation in the form of the functional response. Types I, II, and III functional responses were observed, as were density-independent responses, and these responses varied both among and within fruit species. The highest proportions of fruits were eaten when the Type III functional response was detected, which was when fruit availability was high relative to H. desmarestianus population density. Numerous idiosyncratic influences on seed fate have been documented, but our results indicate that shifts in the numerical and functional responses of seed predators to seasonal and interannual variation in seed availability potentially provide a general mechanistic explanation for patterns of removal and fate for vertebrate-dispersed seeds. ?? 2009 by the Ecological Society of America.

Associations between respiratory health and ambient air quality in Canakkale, Turkey: a long-term cohort study.

PubMed

Mentese, Sibel; Bakar, Coskun; Mirici, Nihal Arzu; Oymak, Sibel; Otkun, Muserref Tatman

2018-05-01

Few epidemiological studies investigating the association between air pollution and health are available in Turkey. The aim of this cohort-type study is to examine the relationships between ambient air quality, respiratory diseases, and decreases in pulmonary function over a year in three different towns in Canakkale: Canakkale Central town (region I), Lapseki town center (region II), and Can town (region III). Region III had four different sub-regions, which were Can town center (region III-A), and the villages located around Can town, namely Durali (region III-B), Kulfal (region III-C), and Yuvalar (region III-D). In the first stage of the study, a detailed questionnaire was completed by the participants (n = 1152) in face-to-face interviews and pulmonary function test (PFT) was performed. In the second stage of the study, PFT measurements were repeated 1 year after the first stage. Particulate matter, SO 2 , NO 2 , and ozone were gathered from air quality monitoring stations located in the centers of the three regions. The most polluted area was region III, while region I and region II were the least polluted areas. The risk of pulmonary function decline throughout a year was 2.1 times higher in region III, 2.4 times higher both in regions III-B and III-C, and 1.6 times higher for smokers in all regions. In the present study, ambient air quality was worse in region III (industrialized region), which influenced PFT scores and the prognostics for chronic respiratory diseases. The findings of this study should be considered for future investment plans in this region related to human and environmental health needs.

Intramembranous valine linked to schizophrenia is required for neuregulin 1 regulation of the morphological development of cortical neurons

PubMed Central

Chen, Yachi; Hancock, Melissa L.; Role, Lorna W.; Talmage, David A.

2010-01-01

Neuregulin 1 (NRG1) signaling is critical to various aspects of neuronal development and function. Among different NRG1 isoforms, the Type III isoforms of NRG1 are unique in their ability to signal via the intracellular domain following γ-secretase-dependent intramembranous processing. However, the functional consequences of Type III NRG1 signaling via its intracellular domain are largely unknown. In this study, we have identified mutations within Type III NRG1 that disrupt intramembranous proteolytic processing and abolish intracellular domain signaling. In particular, substitutions at valine 321, previously linked to schizophrenia risks, result in NRG1 proteins that fail to undergo γ-secretase-mediated nuclear localization and transcriptional activation. Using processing-defective mutants of Type III NRG1, we demonstrate that the intracellular domain signaling is specifically required for NRG1 regulation of the growth and branching of cortical dendrites but not axons. Consistent with the role of Type III NRG1 signaling via the intracellular domain in the initial patterning of cortical dendrites, our findings from pharmacological and genetic studies indicate that Type III NRG1 functions in dendritic development independent of ERBB kinase activity. Taken together, these results support the proposal that aberrant intracellular processing and defective signaling via the intracellular domain of Type III NRG1 impair a subset of NRG1 functions in cortical development and contribute to abnormal neuroconnectivity implicated in schizophrenia. PMID:20610754

Arsenite oxidation by the phyllosphere bacterial community associated with Wolffia australiana.

PubMed

Xie, Wan-Ying; Su, Jian-Qiang; Zhu, Yong-Guan

2014-08-19

Speciation is a key determinant in the toxicity, behavior, and fate of arsenic (As) in the environment. However, little is known about the transformation of As species mediated by floating macrophytes and the phyllosphere bacteria in aquatic and wetland environment. In this study, Wolffia australiana, a rootless floating duckweed, was cultured with (W+B) or without (W-B) phyllosphere bacteria to investigate its ability in arsenite (As(III)) oxidation. Results showed that sterile W. australiana did not oxidize As(III) in the growth medium or in plant tissue, whereas W. australiana with phyllpsphere bacteria displayed substantial As(III) oxidation in the medium. Quantitative PCR of As redox-related functional genes revealed the dominance of the arsenite oxidase (aioA) gene in the phyllosphere bacterial community. These results demonstrate that the phyllosphere bacteria were responsible for the As(III) oxidation in the W+B system. The rapid oxidation of As(III) by the phyllosphere bacterial community may suppress As accumulation in plant tissues under phosphate rich conditions. The aioA gene library showed that the majority of the phyllosphere arsenite-oxidizing bacteria related either closely to unidentified bacteria found in paddy environments or distantly to known arsenite-oxidizing bacteria. Our research suggests a previously overlooked diversity of arsenite-oxidizing bacteria in the phyllosphere of aquatic macrophytes which may have a substantial impact on As biogeochemistry in water environments, warranting further exploration.

The crystal structure of halofantrine-ferriprotoporphyrin IX and the mechanism of action of arylmethanol antimalarials.

PubMed

de Villiers, Katherine A; Marques, Helder M; Egan, Timothy J

2008-08-01

The crystal structure of the complex formed between the antimalarial drug halofantrine and ferriprotoporphyrin IX (Fe(III)PPIX) has been determined by single crystal X-ray diffraction. The structure shows that halofantrine coordinates to the Fe(III) center through its alcohol functionality in addition to pi-stacking of the phenanthrene ring over the porphyrin. The length of the Fe(III)-O bond is consistent with an alkoxide and not an alcohol coordinating group. The iron porphyrin is five coordinate and monomeric. Changes in the electronic spectrum of Fe(III)PPIX upon addition of halofantrine base in acetonitrile solution are almost identical to those observed upon addition of quinidine free base in the same solvent. This suggests homologous binding. Molecular mechanics modeling of Fe(III)PPIX complexes of quinidine, quinine, 9-epiquinine and 9-epiquinidine based on this homology suggests that the antimalarially active quinidine and quinine can readily adopt conformations that permit formation of an intramolecular salt bridge between the protonated quinuclidine tertiary amino group and unprotonated heme propionate group, while the inactive epimers 9-epiquinidine and 9-epiquinine have to adopt high energy conformations in order to accommodate such salt bridge formation. We propose that salt bridge formation may interrupt formation of the hemozoin precursor dimer formed during the heme detoxification pathway and so account for the strong activity of the two active isomers.

The nitrate-reduction gene cluster components exert lineage-dependent contributions to optimization of Sinorhizobium symbiosis with soybeans.

PubMed

Liu, Li Xue; Li, Qin Qin; Zhang, Yun Zeng; Hu, Yue; Jiao, Jian; Guo, Hui Juan; Zhang, Xing Xing; Zhang, Biliang; Chen, Wen Xin; Tian, Chang Fu

2017-12-01

Receiving nodulation and nitrogen fixation genes does not guarantee rhizobia an effective symbiosis with legumes. Here, variations in gene content were determined for three Sinorhizobium species showing contrasting symbiotic efficiency on soybeans. A nitrate-reduction gene cluster absent in S. sojae was found to be essential for symbiotic adaptations of S. fredii and S. sp. III. In S. fredii, the deletion mutation of the nap (nitrate reductase), instead of nir (nitrite reductase) and nor (nitric oxide reductase), led to defects in nitrogen-fixation (Fix - ). By contrast, none of these core nitrate-reduction genes were required for the symbiosis of S. sp. III. However, within the same gene cluster, the deletion of hemN1 (encoding oxygen-independent coproporphyrinogen III oxidase) in both S. fredii and S. sp. III led to the formation of nitrogen-fixing (Fix + ) but ineffective (Eff - ) nodules. These Fix + /Eff - nodules were characterized by significantly lower enzyme activity of glutamine synthetase indicating rhizobial modulation of nitrogen-assimilation by plants. A distant homologue of HemN1 from S. sojae can complement this defect in S. fredii and S. sp. III, but exhibited a more pleotropic role in symbiosis establishment. These findings highlighted the lineage-dependent optimization of symbiotic functions in different rhizobial species associated with the same host. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.

A flow method based on solvent extraction coupled on-line to a reversed micellar mediated chemiluminescence detection for selective determination of gold(III) and gallium(III) in water and industrial samples.

PubMed

Hasanin, Tamer H A; Okamoto, Yasuaki; Fujiwara, Terufumi

2016-02-01

A rapid and sensitive flow method, based on the combination of on-line solvent extraction with reversed micellar mediated chemiluminescence (CL) detection using rhodamine B (RB), was investigated for the selective determination of Au(III) and Ga(III) in aqueous solutions. 2.0 M HCl was the optimum for extracting Au(III) while a 5.0M HCl solution containing 2.5M LiCl was selected as an optimum acidic medium for extraction of Ga(III). The Au(III) and Ga(III) chloro-complex anions were extracted from the above aqueous acidic solutions into toluene as their ion-pair complexes with the protonated RBH(+) ion followed by membrane phase separation in a flow system. In a flow cell of a detector, the extract was mixed with the reversed micellar solution of cetyltrimethylammonium chloride (CTAC) in 1-hexanol-cyclohexane/water (1.0M HCl) containing 0.10 M cerium(IV) and 0.05 M lithium sulfate. Then uptake of the ion-pair by the CTAC reversed micelles and the subsequent CL oxidation of RB with Ce(IV) occurred easily and the CL signals produced were recorded. Using a flow injection system, a detection limit (DL) of 0.4 μM Au(III) and 0.6 μM Ga(III), and linear calibration graphs with dynamic ranges from the respective DLs to 10 μM for Au(III) and Ga(III) were obtained under the optimized experimental conditions. The relative standard deviations (n=6) obtained at 2.0 µM Au(III) and 4.0 µM Ga(III) were 3.0% and 2.4%, respectively. The presented CL methodology has been applied for the determination of Au(III) and Ga(III) in water and industrial samples with satisfactory results. Copyright © 2015 Elsevier B.V. All rights reserved.

Functional defecation disorders in children: comparing the Rome II with the Rome III criteria.

PubMed

Burgers, Rosa; Levin, Alon D; Di Lorenzo, Carlo; Dijkgraaf, Marcel G W; Benninga, Marc A

2012-10-01

To evaluate the prevalence of pediatric functional defecation disorders (FDD) using the Rome III criteria and to compare these data with those obtained using Rome II criteria. A chart review was performed in patients referred to a tertiary outpatient clinic with symptoms of constipation and/or fecal incontinence. All patients received a standardized bowel questionnaire and physical examination, including rectal examination. The prevalence of pediatric FDD according to both Rome criteria sets was assessed. Patients with FDD (n = 336; 61% boys, mean age 6.3 ± 3.5 SD) were studied: 39% had a defecation frequency ≤ 2/wk, 75% had fecal incontinence, 75% displayed retentive posturing, 60% had pain during defecation, 49% passed large diameter stools, and 49% had a palpable rectal fecal mass. According to the Rome III criteria, 87% had functional constipation (FC) compared with only 34% fulfilling criteria for either FC or functional fecal retention based on the Rome II definitions (P < .001). Of the patients with a rectal fecal mass, 95% would also have been correctly identified as having FC without a rectal examination. Twenty-nine patients (11%) fulfilled the criteria for functional nonretentive fecal incontinence according to both the Rome II and Rome III criteria. The pediatric Rome III criteria for FC are less restrictive than the Rome II criteria. The Rome III criteria are an important step forward in the definition and recognition of FDD in children. Copyright © 2012 Mosby, Inc. All rights reserved.

Axially deformed solution of the Skyrme–Hartree–Fock–Bogolyubov equations using the transformed harmonic oscillator basis (III) hfbtho (v3.00): A new version of the program

DOE PAGES

Perez, R. Navarro; Schunck, N.; Lasseri, R. -D.; ...

2017-07-05

Here, we describe the new version 3.00 of the code hfbtho that solves the nuclear Hartree–Fock (HF) or Hartree–Fock–Bogolyubov (HFB) problem by using the cylindrical transformed deformed harmonic oscillator basis. In the new version, we have implemented the following features: (i) the full Gogny force in both particle–hole and particle–particle channels, (ii) the calculation of the nuclear collective inertia at the perturbative cranking approximation, (iii) the calculation of fission fragment charge, mass and deformations based on the determination of the neck, (iv) the regularization of zero-range pairing forces, (v) the calculation of localization functions, (vi) a MPI interface for large-scalemore » mass table calculations.« less

Type III Nrg1 back signaling enhances functional TRPV1 along sensory axons contributing to basal and inflammatory thermal pain sensation.

PubMed

Canetta, Sarah E; Luca, Edlira; Pertot, Elyse; Role, Lorna W; Talmage, David A

2011-01-01

Type III Nrg1, a member of the Nrg1 family of signaling proteins, is expressed in sensory neurons, where it can signal in a bi-directional manner via interactions with the ErbB family of receptor tyrosine kinases (ErbB RTKs). Type III Nrg1 signaling as a receptor (Type III Nrg1 back signaling) can acutely activate phosphatidylinositol-3-kinase (PtdIns3K) signaling, as well as regulate levels of α7* nicotinic acetylcholine receptors, along sensory axons. Transient receptor potential vanilloid 1 (TRPV1) is a cation-permeable ion channel found in primary sensory neurons that is necessary for the detection of thermal pain and for the development of thermal hypersensitivity to pain under inflammatory conditions. Cell surface expression of TRPV1 can be enhanced by activation of PtdIns3K, making it a potential target for regulation by Type III Nrg1. We now show that Type III Nrg1 signaling in sensory neurons affects functional axonal TRPV1 in a PtdIns3K-dependent manner. Furthermore, mice heterozygous for Type III Nrg1 have specific deficits in their ability to respond to noxious thermal stimuli and to develop capsaicin-induced thermal hypersensitivity to pain. Cumulatively, these results implicate Type III Nrg1 as a novel regulator of TRPV1 and a molecular mediator of nociceptive function.

Determinants of Conflict in the Philippines

DTIC Science & Technology

2012-06-01

CONFLICT IN THE PHILIPPINES by Jesus P. Durante III June 2012 Thesis Co-Advisors Nancy Roberts Sean Everton Second Reader: Kristen...Jesus P. Durante III 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) Naval Postgraduate School Monterey, CA 93943-5000 8. PERFORMING...release, distribution is unlimited DETERMINANTS OF CONFLICT IN THE PHILIPPINES Jesus P. Durante III Lieutenant Colonel, Philippine Army B.S

25 CFR 291.7 - What must the Secretary do if it has been determined that the Indian tribe is eligible to request...

Code of Federal Regulations, 2010 CFR

2010-04-01

... the Indian tribe is eligible to request Class III gaming procedures? 291.7 Section 291.7 Indians BUREAU OF INDIAN AFFAIRS, DEPARTMENT OF THE INTERIOR ECONOMIC ENTERPRISES CLASS III GAMING PROCEDURES... request Class III gaming procedures? (a) If the Secretary determines that the Indian tribe is eligible to...

Expression of synaptogyrin-1 in T1R2-expressing type II taste cells and type III taste cells of rat circumvallate taste buds.

PubMed

Kotani, Takeshi; Toyono, Takashi; Seta, Yuji; Kitou, Ayae; Kataoka, Shinji; Toyoshima, Kuniaki

2013-09-01

Synaptogyrins are conserved components of the exocytic apparatus and function as regulators of Ca(2+)-dependent exocytosis. The synaptogyrin family comprises three isoforms: two neuronal (synaptogyrin-1 and -3) and one ubiquitous (synaptogyrin-2) form. Although the expression patterns of the exocytic proteins synaptotagmin-1, SNAP-25, synaptobrevin-2 and synaptophysin have been elucidated in taste buds, the function and expression pattern of synaptogyrin-1 in rat gustatory tissues have not been determined. Therefore, we examined the expression patterns of synaptogyrin-1 and several cell-specific markers of type II and III cells in rat gustatory tissues. Reverse transcription/polymerase chain reaction assays and immunoblot analysis revealed the expression of synaptogyrin-1 mRNA and its protein in circumvallate papillae. In fungiform, foliate and circumvallate papillae, the antibody against synaptogyrin-1 immunolabeled a subset of taste bud cells and intra- and subgemmal nerve processes. Double-labeling experiments revealed the expression of synaptogyrin-1 in most taste cells immunoreactive for aromatic L-amino acid decarboxylase and the neural cell adhesion molecule. A subset of synaptogyrin-1-immunoreactive taste cells also expressed phospholipase Cβ2, gustducin, or sweet taste receptor (T1R2). In addition, most synaptogyrin-1-immunoreactive taste cells expressed synaptobrevin-2. These results suggest that synaptogyrin-1 plays a regulatory role in transmission at the synapses of type III cells and is involved in exocytic function with synaptobrevin-2 in a subset of type II cells in rat taste buds.

Chemometrics-assisted simultaneous determination of cobalt(II) and chromium(III) with flow-injection chemiluminescence method

NASA Astrophysics Data System (ADS)

Li, Baoxin; Wang, Dongmei; Lv, Jiagen; Zhang, Zhujun

2006-09-01

In this paper, a flow-injection chemiluminescence (CL) system is proposed for simultaneous determination of Co(II) and Cr(III) with partial least squares calibration. This method is based on the fact that both Co(II) and Cr(III) catalyze the luminol-H 2O 2 CL reaction, and that their catalytic activities are significantly different on the same reaction condition. The CL intensity of Co(II) and Cr(III) was measured and recorded at different pH of reaction medium, and the obtained data were processed by the chemometric approach of partial least squares. The experimental calibration set was composed with nine sample solutions using orthogonal calibration design for two component mixtures. The calibration curve was linear over the concentration range of 2 × 10 -7 to 8 × 10 -10 and 2 × 10 -6 to 4 × 10 -9 g/ml for Co(II) and Cr(III), respectively. The proposed method offers the potential advantages of high sensitivity, simplicity and rapidity for Co(II) and Cr(III) determination, and was successfully applied to the simultaneous determination of both analytes in real water sample.

Use of responder threshold criteria to evaluate the response to treatment in the phase III CHEST-1 study.

PubMed

D'Armini, Andrea M; Ghofrani, Hossein-Ardeschir; Kim, Nick H; Mayer, Eckhard; Morsolini, Marco; Pulido-Zamudio, Tomás; Simonneau, Gerald; Wilkins, Martin R; Curram, John; Davie, Neil; Hoeper, Marius M

2015-03-01

In the Chronic Thromboembolic Pulmonary Hypertension Soluble Guanylate Cyclase - Stimulator Trial 1 (CHEST-1) study, riociguat improved 6-minute walking distance (6MWD) vs placebo in patients with inoperable chronic thromboembolic pulmonary hypertension or persistent/recurrent pulmonary hypertension after pulmonary endarterectomy. In this study, the proportion of patients who achieved responder thresholds that correlate with improved outcome in patients with pulmonary arterial hypertension was determined at baseline and at the end of CHEST-1. Patients received placebo or riociguat individually adjusted up to 2.5 mg 3 times a day for 16 weeks. Response criteria were defined as follows: 6MWD increase ≥40 m, 6MWD ≥380 m, cardiac index ≥2.5 liters/min/m(2), pulmonary vascular resistance <500 dyn∙sec∙cm(-5), mixed venous oxygen saturation ≥65%, World Health Organization functional class I/II, N-terminal pro-brain natriuretic peptide <1,800 pg/ml, and right atrial pressure <8 mm Hg. Riociguat increased the proportion of patients with 6MWD ≥380 m, World Health Organization functional class I/II, and pulmonary vascular resistance <500 dyn∙sec∙cm(-5) from 37%, 34%, and 25% at baseline to 58%, 57%, and 50% at Week 16, whereas there was little change in placebo-treated patients (6MWD ≥380 m, 43% vs 44%; World Health Organization functional class I/II, 29% vs 38%; pulmonary vascular resistance <500 dyn∙sec∙cm(-5), 27% vs 26%). Similar changes were observed for thresholds for cardiac index, mixed venous oxygen saturation, N-terminal pro-brain natriuretic peptide, and right atrial pressure. In this exploratory analysis, riociguat increased the proportion of patients with inoperable chronic thromboembolic pulmonary hypertension or persistent/recurrent pulmonary hypertension after pulmonary endarterectomy achieving criteria defining a positive response to therapy. Copyright © 2015 International Society for Heart and Lung Transplantation. Published by Elsevier Inc. All rights reserved.

Preseason Functional Test Scores Are Associated With Future Sports Injury in Female Collegiate Athletes.

PubMed

Brumitt, Jason; Heiderscheit, Bryan C; Manske, Robert C; Niemuth, Paul E; Mattocks, Alma; Rauh, Mitchell J

2018-06-01

Brumitt, J, Heiderscheit, B, Manske, R, Niemuth, PE, Mattocks, A, and Rauh, MJ. Preseason functional test scores are associated with future sports injury in female collegiate athletes. J Strength Cond Res 32(6): 1692-1701, 2018-Recent prospective cohort studies have reported preseason functional performance test (FPT) measures and associations with future risk of injury; however, the findings associated with these studies have been equivocal. The purpose of this study was to determine the ability of a battery of FPTs as a preseason screening tool to identify female Division III (D III) collegiate athletes who may be at risk for a noncontact time-loss injury to the lower quadrant (LQ = low back and lower extremities). One hundred six female D III athletes were recruited for this study. Athletes performed 3 FPTs: standing long jump (SLJ), single-leg hop (SLH) for distance, and the lower extremity functional test (LEFT). Time-loss sport-related injuries were tracked during the season. Thirty-two (24 initial and 8 subsequent) time-loss LQ injuries were sustained during the study. Ten of the 24 initial injuries occurred at the thigh and knee. At-risk athletes with suboptimal FPT measures (SLJ ≤79% ht; (B) SLH ≤64% ht; LEFT ≥118 seconds) had significantly greater rates of initial (7.2 per 1,000 athletic exposures [AEs]) and total (7.6 per 1,000 AEs) time-loss thigh or knee injuries than the referent group (0.9 per 1,000 AEs; 1.0 per 1,000 AEs, respectively). At-risk athletes were 9 times more likely to experience a thigh or knee injury (odds ratio [OR] = 9.7, confidence interval [CI]: 2.3-39.9; p = 0.002) than athletes in the referent group. At-risk athletes with a history of LQ sports injury and lower off-season training habits had an 18-fold increased risk of a time-loss thigh or knee injury during the season (adjusted OR = 18.7, CI: 3.0-118.1; p = 0.002). This battery of FPTs appears useful as a tool for identifying female D III athletes at risk of an LQ injury, especially to the thigh or knee region.

Induction of intracellular Ca2+ and pH changes in Sf9 insect cells by rhodojaponin-III, a natural botanic insecticide isolated from Rhododendron molle.

PubMed

Cheng, Xing-An; Xie, Jian-Jun; Hu, Mei-Ying; Zhang, Yan-Bo; Huang, Jing-Fei

2011-04-15

Many studies on intracellular calcium ([Ca2+](i)) and intracellular pH (pH(i)) have been carried out due to their importance in regulation of different cellular functions. However, most of the previous studies are focused on human or mammalian cells. The purpose of the present study was to characterize the effect of Rhodojaponin-III (R-III) on [Ca2+](i) and pH(i) and the proliferation of Sf9 cells. R-III strongly inhibited Sf9 cells proliferation with a time- and dose-dependent manner. Flow cytometry established that R-III interfered with Sf9 cells division and arrested them in G2/M. By using confocal scanning technique, effects of R-III on intracellular free calcium ([Ca2+](i)) and intracellular pH (pH(i)) in Sf9 cells were determined. R-III induced a significant dose-dependent (1, 10, 100, 200 μg/mL) increase in [Ca2+](i) and pH(i) of Sf9 cells in presence of Ca2+-containing solution (Hanks) and an irreversible decrease in the absence of extra cellular Ca2+. We also found that both extra cellular Ca2+ and intracellular Ca2+ stores contributed to the increase of [Ca2+](i), because completely treating Sf9 cells with CdCl(2) (5 mM), a Ca2+ channels blocker, R-III (100 μg/mL) induced a transient elevation of [Ca2+](i) in case of cells either in presence of Ca2+ containing or Ca2+ free solution. In these conditions, pH(i) showed similar changes with that of [Ca2+](i) on the whole. Accordingly, we supposed that there was a certain linkage for change of [Ca2+](i), cell cycle arrest, proliferation inhibition in Sf9 cells induced by R-III.

Contractility in type III cochlear fibrocytes is dependent on non-muscle myosin II and intercellular gap junctional coupling.

PubMed

Kelly, John J; Forge, Andrew; Jagger, Daniel J

2012-08-01

The cochlear spiral ligament is a connective tissue that plays diverse roles in normal hearing. Spiral ligament fibrocytes are classified into functional sub-types that are proposed to carry out specialized roles in fluid homeostasis, the mediation of inflammatory responses to trauma, and the fine tuning of cochlear mechanics. We derived a secondary sub-culture from guinea pig spiral ligament, in which the cells expressed protein markers of type III or "tension" fibrocytes, including non-muscle myosin II (nmII), α-smooth muscle actin (αsma), vimentin, connexin43 (cx43), and aquaporin-1. The cells formed extensive stress fibers containing αsma, which were also associated intimately with nmII expression, and the cells displayed the mechanically contractile phenotype predicted by earlier modeling studies. cx43 immunofluorescence was evident within intercellular plaques, and the cells were coupled via dye-permeable gap junctions. Coupling was blocked by meclofenamic acid (MFA), an inhibitor of cx43-containing channels. The contraction of collagen lattice gels mediated by the cells could be prevented reversibly by blebbistatin, an inhibitor of nmII function. MFA also reduced the gel contraction, suggesting that intercellular coupling modulates contractility. The results demonstrate that these cells can impart nmII-dependent contractile force on a collagenous substrate, and support the hypothesis that type III fibrocytes regulate tension in the spiral ligament-basilar membrane complex, thereby determining auditory sensitivity.

APOC3 -482C>T polymorphism, circulating apolipoprotein C-III and smoking: interrelation and roles in predicting type-2 diabetes and coronary disease.

PubMed

Onat, Altan; Erginel-Unaltuna, Nihan; Coban, Neslihan; Ciçek, Gökhan; Yüksel, Hüsniye

2011-04-01

We determined the relationship of smoking status on APOC3 -482C>T polymorphism and apolipoprotein C-III (apoC-III) concentrations and the latter two parameters' influence on risk of diabetes and coronary heart disease (CHD). Prediction of incident cases was assessed at 5.5years' follow-up in unselected 519 individuals of a general population genotyped for -482C>T polymorphism. Female sex and current smoking were significantly associated with low circulating apoC-III in subjects without (p≤0.033) than with abdominal obesity (p=0.053) or than insulin resistant -482TT homozygotes (p=0.034) who had 20-30% higher serum apoC-III. Multi-adjusted serum apoC-III was log-linearly associated with fasting triglycerides. ApoC-III levels determined the development of diabetes [RR 1.56 (95%CI 1.21; 2.01)] and CHD [RR 1.38 (1.10; 1.72) for an increment of 14%], after adjustment for confounders. APOC3 -482TT genotype is associated with high apoC-III concentrations only in the presence of abdominal obesity or insulin resistance, but not in current smokers who remain lean or insulin-sensitive. Rather than APOC3 -482C>T polymorphism, circulating apoC-III determines cardiometabolic risk. Copyright © 2011 The Canadian Society of Clinical Chemists. Published by Elsevier Inc. All rights reserved.

Behind the lines–actions of bacterial type III effector proteins in plant cells

PubMed Central

Büttner, Daniela

2016-01-01

Pathogenicity of most Gram-negative plant-pathogenic bacteria depends on the type III secretion (T3S) system, which translocates bacterial effector proteins into plant cells. Type III effectors modulate plant cellular pathways to the benefit of the pathogen and promote bacterial multiplication. One major virulence function of type III effectors is the suppression of plant innate immunity, which is triggered upon recognition of pathogen-derived molecular patterns by plant receptor proteins. Type III effectors also interfere with additional plant cellular processes including proteasome-dependent protein degradation, phytohormone signaling, the formation of the cytoskeleton, vesicle transport and gene expression. This review summarizes our current knowledge on the molecular functions of type III effector proteins with known plant target molecules. Furthermore, plant defense strategies for the detection of effector protein activities or effector-triggered alterations in plant targets are discussed. PMID:28201715

Connective tissue-activating peptide III: a novel blood biomarker for early lung cancer detection.

PubMed

Yee, John; Sadar, Marianne D; Sin, Don D; Kuzyk, Michael; Xing, Li; Kondra, Jennifer; McWilliams, Annette; Man, S F Paul; Lam, Stephen

2009-06-10

There are no reliable blood biomarkers to detect early lung cancer. We used a novel strategy that allows discovery of differentially present proteins against a complex and variable background. Mass spectrometry analyses of paired pulmonary venous-radial arterial blood from 16 lung cancer patients were applied to identify plasma proteins potentially derived from the tumor microenvironment. Two differentially expressed proteins were confirmed in 64 paired venous-arterial blood samples using an immunoassay. Twenty-eight pre- and postsurgical resection peripheral blood samples and two independent, blinded sets of plasma from 149 participants in a lung cancer screening study (49 lung cancers and 100 controls) and 266 participants from the National Heart Lung and Blood Institute Lung Health Study (45 lung cancer and 221 matched controls) determined the accuracy of the two protein markers to detect subclinical lung cancer. Connective tissue-activating peptide III (CTAP III)/ neutrophil activating protein-2 (NAP-2) and haptoglobin were identified to be significantly higher in venous than in arterial blood. CTAP III/NAP-2 levels decreased after tumor resection (P = .01). In two independent population cohorts, CTAP III/NAP-2 was significantly associated with lung cancer and improved the accuracy of a lung cancer risk prediction model that included age, smoking, lung function (FEV(1)), and an interaction term between FEV(1) and CTAP III/NAP-2 (area under the curve, 0.84; 95% CI, 0.77 to 0.91) compared to CAPIII/NAP-2 alone. We identified CTAP III/NAP-2 as a novel biomarker to detect preclinical lung cancer. The study underscores the importance of applying blood biomarkers as part of a multimodal lung cancer risk prediction model instead of as stand-alone tests.

LAT1 targeted delivery of methionine based imaging probe derived from M(III) metal ions for early diagnosis of proliferating tumours using molecular imaging modalities.

PubMed

Hazari, Puja Panwar; Prakash, Surbhi; Meena, Virendra K; Jaswal, Ambika; Khurana, Harleen; Mishra, Surabhi Kirti; Bhonsle, Hemanth Kumar; Singh, Lokendra; Mishra, Anil K

2015-01-01

We investigated the potential of DTPA-bis(Methionine), a target specific amino acid based probe for detection of L-type amino acid transporters (LAT1) known to over express in proliferating tumours using multimodality imaging. The ligand, DTPA-bis(Met) was readily converted to lanthanide complexes and was found capable of targeting cancer cells using multimodality imaging. DTPA-bis(Met) complexes were synthesized and characterized by mass spectroscopy. MR longitudinal relaxivity, r₁ = 4.067 ± 0.31 mM⁻¹s⁻¹ and transverse relaxivity, r₂ = 8.61 ± 0.07 mM⁻¹s⁻¹ of Gd(III)-DTPA-bis(Met) were observed at pH 7.4 at 7 T. Bright, localized fluorescence of Eu(III)-DTPA-bis(Met) was observed with standard microscopy and displacement studies indicated ligand functionality. K(D) value determined for Eu(III)-DTPA-bis(Met) on U-87 MG cells was found to be 17.3 pM and showed appreciable fluorescence within the cells. Radio HPLC showed a radiochemical purity more than 95% (specific activity = 400-500 MBq/μmol, labelling efficiency 78 %) for ⁶⁸Ga(III)-DTPA-bis(Met). Pre-treatment of xenografted U-87 MG athymic mice with ⁶⁸Ga(III)-DTPA-bis(Met) following unlabelled L-methionine administration reduced tumour uptake by 10-folds in Micro PET. These data support the specific binding of ⁶⁸Ga(III)-DTPA-bis(Met) to the LAT1 transporter. To summarize, this agent possesses high stability in biological environment and exhibits effective interaction with its LAT1 transporters giving high accumulation in tumour area, excellent tumour/non-tumour ratio and low non-specific retention in vivo.

Extractive photometric determination of gold(III) with 1-(2',4',6'-trichlorophenyl)-4,4,6-trimethyl-(1H,4H)-2-pyrimidinethiol in presence of tri-iso-octylamine.

PubMed

Amuse, M A; Kuchekar, S R; Mote, N A; Chavan, M B

1985-10-01

Tervalent gold was determined spectrophotometrically as its anionic 1:4 gold-thiol complex extracted into chloroform from aqueous acidic medium (1.5M sulphuric acid) in the presence of tri-iso-octylamine. The complex exhibits maximum absorption at 480 nm (molar absorptivity 4.60 x 10(3) l.mole(-1).cm(-1)) and Beer's law is obeyed in the concentration range 5-50 microg of gold(III) per ml. The relative standard deviation and relative error, calculated from ten determinations of solutions containing 15 microg of gold(III) per ml were 1.0% and 0.8%. The method is simple, selective and reproducible. It permits separation of gold(III) from associated elements and its determination in synthetic mixtures.

STRUCTURAL AND FUNCTIONAL CONSEQUENCES OF CIRCULAR PERMUTATION ON THE ACTIVE SITE OF OLD YELLOW ENZYME.

PubMed

Daugherty, Ashley B; Horton, John R; Cheng, Xiaodong; Lutz, Stefan

2015-02-06

Circular permutation of the NADPH-dependent oxidoreductase Old Yellow Enzyme from Saccharomyces pastorianus (OYE1) can significantly enhance the enzyme's catalytic performance. Termini relocation into four regions of the protein (sectors I-IV) near the active site has proven effective in altering enzyme function. To better understand the structural consequences and rationalize the observed functional gains in these OYE1 variants, we selected representatives from sectors I-III for further characterization by biophysical methods and X-ray crystallography. These investigations not only show trends in enzyme stability and quaternary structure as a function of termini location, but also provide a possible explanation for the catalytic gains in our top-performing OYE variant (new N-terminus at residue 303; sector III). Crystallographic analysis indicates that termini relocation into sector III affects the loop β6 region (amino acid positions: 290-310) of OYE1 which forms a lid over the active site. Peptide backbone cleavage greatly enhances local flexibility, effectively converting the loop into a tether and consequently increasing the environmental exposure of the active site. Interestingly, such active site remodeling does not negatively impact the enzyme's activity and stereoselectivity, nor does it perturb the conformation of other key active site residues with the exception of Y375. These observations were confirmed in truncation experiments, deleting all residues of the loop β6 region in our OYE variant. Intrigued by the finding that circular permutation leaves most of the key catalytic residues unchanged, we also tested OYE permutants for possible additive or synergistic effects of amino acid substitutions. Distinct functional changes in these OYE variants were detected upon mutations at W116, known in native OYE1 to cause inversion of diastereo-selectivity for ( S )-carvone reduction. Our findings demonstrate the contribution of loop β6 toward determining the stereoselectivity of OYE1, an important insight for future OYE engineering efforts.

Structural and Functional Consequences of Circular Permutation on the Active Site of Old Yellow Enzyme

DOE PAGES

Daugherty, Ashley B.; Horton, John R.; Cheng, Xiaodong; ...

2014-12-09

Circular permutation of the NADPH-dependent oxidoreductase Old Yellow Enzyme from Saccharomyces pastorianus (OYE1) can significantly enhance the enzyme’s catalytic performance. Termini relocation into four regions of the protein (sectors I–IV) near the active site has proven effective in altering enzyme function. To better understand the structural consequences and rationalize the observed functional gains in these OYE1 variants, we selected representatives from sectors I–III for further characterization by biophysical methods and X-ray crystallography. These investigations not only show trends in enzyme stability and quaternary structure as a function of termini location but also provide a possible explanation for the catalytic gainsmore » in our top-performing OYE variant (new N-terminus at residue 303; sector III). Crystallographic analysis indicates that termini relocation into sector III affects the loop β6 region (amino acid positions: 290–310) of OYE1, which forms a lid over the active site. Peptide backbone cleavage greatly enhances local flexibility, effectively converting the loop into a tether and consequently increasing the environmental exposure of the active site. Interestingly, such an active site remodeling does not negatively impact the enzyme’s activity and stereoselectivity; neither does it perturb the conformation of other key active site residues with the exception of Y375. These observations were confirmed in truncation experiments, deleting all residues of the loop β6 region in our OYE variant. Intrigued by the finding that circular permutation leaves most of the key catalytic residues unchanged, we also tested OYE permutants for possible additive or synergistic effects of amino acid substitutions. Distinct functional changes in these OYE variants were detected upon mutations at W116, known in native OYE1 to cause inversion of diastereoselectivity for (S)-carvone reduction. In conclusion, our findings demonstrate the contribution of loop β6 toward determining the stereoselectivity of OYE1, an important insight for future OYE engineering efforts.« less

NMR structural studies of the supramolecular adducts between a liver cytosolic bile acid binding protein and gadolinium(III)-chelates bearing bile acids residues: molecular determinants of the binding of a hepatospecific magnetic resonance imaging contrast agent.

PubMed

Assfalg, Michael; Gianolio, Eliana; Zanzoni, Serena; Tomaselli, Simona; Russo, Vito Lo; Cabella, Claudia; Ragona, Laura; Aime, Silvio; Molinari, Henriette

2007-11-01

The binding affinities of a selected series of Gd(III) chelates bearing bile acid residues, potential hepatospecific MRI contrast agents, to a liver cytosolic bile acid transporter, have been determined through relaxivity measurements. The Ln(III) complexes of compound 1 were selected for further NMR structural analysis aimed at assessing the molecular determinants of binding. A number of NMR experiments have been carried out on the bile acid-like adduct, using both diamagnetic Y(III) and paramagnetic Gd(III) complexes, bound to a liver bile acid binding protein. The identified protein "hot spots" defined a single binding site located at the protein portal region. The presented findings will serve in a medicinal chemistry approach for the design of hepatocytes-selective gadolinium chelates for liver malignancies detection.

Selective determination of arsenic(III) and arsenic(V) with ammonium pyrrolidinedithiocarbamate, sodium diethyldithiocarbamate and dithizone by means of flameless atomic-absorption spectrophotometry with a carbon-tube atomizer.

PubMed

Kamada, T

The extraction behaviour of arsenic(III) and arsenic(V) with ammonium pyrrolidinedithiocarbamate, sodium diethyldithiocarbamate and dithizone in organic solvents has been investigated by means of nameless atomic-absorption spectrophotometry with a carbon-tube atomizer. The selective extraction of arsenic(III) and differential determination of arsenic(III) and arsenic(V) have been developed. With ammonium pyrrolidinedithiocarbamate and methyl isobutyl ketone or nitrobenzene, when the aqueous phase/solvent volume ratio is 5 and the injection volume in the carbon tube is 20 mul, the sensitivities for 1% absorption are 0.4 and 0.5 part per milliard of arsenic, respectively. The relative standard deviations are ca. 3%. Interference by many metal ions can be prevented by masking with EDTA. The proposed methods are applied satisfactorily for determination of As(III) and As(V) in various types of water.

Acetylcholinesterase inhibition-based biosensor for aluminum(III) chronoamperometric determination in aqueous media.

PubMed

Barquero-Quirós, Miriam; Domínguez-Renedo, Olga; Alonso-Lomillo, Maria Asunción; Arcos-Martínez, María Julia

2014-05-07

A novel amperometric biosensor for the determination of Al(III) based on the inhibition of the enzyme acetylcholinesterase has been developed. The immobilization of the enzyme was performed on screen-printed carbon electrodes modified with gold nanoparticles. The oxidation signal of acetylthiocholine iodide enzyme substrate was affected by the presence of Al(III) ions leading to a decrease in the amperometric current. The developed system has a detection limit of 2.1 ± 0.1 μM for Al(III). The reproducibility of the method is 8.1% (n = 4). Main interferences include Mo(VI), W(VI) and Hg(II) ions. The developed method was successfully applied to the determination of Al(III) in spiked tap water . The analysis of a certified standard reference material was also carried out. Both results agree with the certified values considering the respective associated uncertainties.

Acetylcholinesterase Inhibition-Based Biosensor for Aluminum(III) Chronoamperometric Determination in Aqueous Media

PubMed Central

Barquero-Quirós, Miriam; Domínguez-Renedo, Olga; Alonso-Lomillo, Maria Asunción; Arcos-Martínez, María Julia

2014-01-01

A novel amperometric biosensor for the determination of Al(III) based on the inhibition of the enzyme acetylcholinesterase has been developed. The immobilization of the enzyme was performed on screen-printed carbon electrodes modified with gold nanoparticles. The oxidation signal of acetylthiocholine iodide enzyme substrate was affected by the presence of Al(III) ions leading to a decrease in the amperometric current. The developed system has a detection limit of 2.1 ± 0.1 μM for Al(III). The reproducibility of the method is 8.1% (n = 4). Main interferences include Mo(VI), W(VI) and Hg(II) ions. The developed method was successfully applied to the determination of Al(III) in spiked tap water. The analysis of a certified standard reference material was also carried out. Both results agree with the certified values considering the respective associated uncertainties. PMID:24811076

Novel Luminescent Probe Based on a Terbium(III) Complex for Hemoglobin Determination

NASA Astrophysics Data System (ADS)

Yegorova, A. V.; Leonenko, I. I.; Aleksandrova, D. I.; Scrypynets, Yu. V.; Antonovich, V. P.; Ukrainets, I. V.

2014-09-01

We have studied the spectral luminescent properties of Tb(III) and Eu(III) complexes with a number of novel derivatives of oxoquinoline-3-carboxylic acid amides (L1-L5 ). We have observed quenching of the luminescence of 1:1 Tb(III)-L1-5 complexes by hemoglobin (Hb), which is explained by resonance energy transfer of electronic excitation from the donor (Tb(III)-L1-5 ) to the acceptor (Hb). Using the novel luminescent probe Tb(III)-L1, we have developed a method for determining Hb in human blood. The calibration Stern-Volmer plot is linear in the Hb concentration range 0.6-36.0 μg/mL, detection limit 0.2 μg/mL (3·10-9 mol/L).

Molten-Salt-Based Growth of Group III Nitrides

DOEpatents

Waldrip, Karen E.; Tsao, Jeffrey Y.; Kerley, Thomas M.

2008-10-14

A method for growing Group III nitride materials using a molten halide salt as a solvent to solubilize the Group-III ions and nitride ions that react to form the Group III nitride material. The concentration of at least one of the nitride ion or Group III cation is determined by electrochemical generation of the ions.

Steric and Electronic Influence on Proton-Coupled Electron-Transfer Reactivity of a Mononuclear Mn(III)-Hydroxo Complex.

PubMed

Rice, Derek B; Wijeratne, Gayan B; Burr, Andrew D; Parham, Joshua D; Day, Victor W; Jackson, Timothy A

2016-08-15

A mononuclear hydroxomanganese(III) complex was synthesized utilizing the N5 amide-containing ligand 2-[bis(pyridin-2-ylmethyl)]amino-N-2-methyl-quinolin-8-yl-acetamidate (dpaq(2Me) ). This complex is similar to previously reported [Mn(III)(OH)(dpaq(H))](+) [Inorg. Chem. 2014, 53, 7622-7634] but contains a methyl group adjacent to the hydroxo moiety. This α-methylquinoline group in [Mn(III)(OH)(dpaq(2Me))](+) gives rise to a 0.1 Å elongation in the Mn-N(quinoline) distance relative to [Mn(III)(OH)(dpaq(H))](+). Similar bond elongation is observed in the corresponding Mn(II) complex. In MeCN, [Mn(III)(OH)(dpaq(2Me))](+) reacts rapidly with 2,2',6,6'-tetramethylpiperidine-1-ol (TEMPOH) at -35 °C by a concerted proton-electron transfer (CPET) mechanism (second-order rate constant k2 of 3.9(3) M(-1) s(-1)). Using enthalpies and entropies of activation from variable-temperature studies of TEMPOH oxidation by [Mn(III)(OH)(dpaq(2Me))](+) (ΔH(‡) = 5.7(3) kcal(-1) M(-1); ΔS(‡) = -41(1) cal M(-1) K(-1)), it was determined that [Mn(III)(OH)(dpaq(2Me))](+) oxidizes TEMPOH ∼240 times faster than [Mn(III)(OH)(dpaq(H))](+). The [Mn(III)(OH)(dpaq(2Me))](+) complex is also capable of oxidizing the stronger O-H and C-H bonds of 2,4,6-tri-tert-butylphenol and xanthene, respectively. However, for these reactions [Mn(III)(OH)(dpaq(2Me))](+) displays, at best, modest rate enhancement relative to [Mn(III)(OH)(dpaq(H))](+). A combination of density function theory (DFT) and cyclic voltammetry studies establish an increase in the Mn(III)/Mn(II) reduction potential of [Mn(III)(OH)(dpaq(2Me))](+) relative to [Mn(III)(OH)(dpaq(H))](+), which gives rise to a larger driving force for CPET for the former complex. Thus, more favorable thermodynamics for [Mn(III)(OH)(dpaq(2Me))](+) can account for the dramatic increase in rate with TEMPOH. For the more sterically encumbered substrates, DFT computations suggest that this effect is mitigated by unfavorable steric interactions between the substrate and the α-methylquinoline group of the dpaq(2Me) ligand. The DFT calculations, which reproduce the experimental activation free energies quite well, provide the first examination of the transition-state structure of mononuclear Mn(III)(OH) species during a CPET reaction.

Test–Retest Variability of Functional and Structural Parameters in Patients with Stargardt Disease Participating in the SAR422459 Gene Therapy Trial

PubMed Central

Parker, Maria A.; Choi, Dongseok; Erker, Laura R.; Pennesi, Mark E.; Yang, Paul; Chegarnov, Elvira N.; Steinkamp, Peter N.; Schlechter, Catherine L.; Dhaenens, Claire-Marie; Mohand-Said, Saddek; Audo, Isabelle; Sahel, Jose; Weleber, Richard G.; Wilson, David J.

2016-01-01

Purpose The goal of this analysis was to determine the test–retest variability of functional and structural measures from a cohort of patients with advanced forms of Stargardt Disease (STGD) participating in the SAR422459 (NCT01367444) gene therapy clinical trial. Methods Twenty-two participants, aged 24 to 66, diagnosed with advanced forms of STGD, with at least one pathogenic ABCA4 mutation on each chromosome participating in the SAR422459 (NCT01367444) gene therapy clinical trial, were screened over three visits within 3 weeks or less. Functional visual evaluations included: best-corrected visual acuity (BCVA) Early Treatment Diabetic Retinopathy Study (ETDRS) letter score, semiautomated kinetic perimetry (SKP) using isopters I4e, III4e, and V4e, hill of vision (HOV) calculated from static visual fields (SVF) by using a 184n point centrally condensed grid with the stimulus size V test target. Retinal structural changes such as central macular thickness and macular volume were assessed by spectral-domain optical coherence tomography (SD-OCT). Repeatability coefficients (RC) and 95% confidential intervals (CI) were calculated for each parameter using a hierarchical mixed-effects model and bootstrapping. Results Criteria for statistically significant changes for various parameters were found to be the following: BCVA letter score (8 letters), SKP isopters I4e, III4e, and V4e (3478.85; 2488.02 and 2622.46 deg2, respectively), SVF full volume HOV (VTOT, 14.62 dB-sr), central macular thickness, and macular volume (4.27 μm and 0.15 mm3, respectively). Conclusions This analysis provides important information necessary to determine if significant changes are occurring in structural and functional assessments commonly used to measure disease progression in this cohort of patients with STGD. Moreover, this information is useful for future trials assessing safety and efficacy of treatments in STGD. Translational Relevance Determination of variability of functional and structural measures in participants with advanced stages of the STGD is necessary to assess efficacy and safety in treatment trials involving STGD patients. PMID:27730010

Test-Retest Variability of Functional and Structural Parameters in Patients with Stargardt Disease Participating in the SAR422459 Gene Therapy Trial.

PubMed

Parker, Maria A; Choi, Dongseok; Erker, Laura R; Pennesi, Mark E; Yang, Paul; Chegarnov, Elvira N; Steinkamp, Peter N; Schlechter, Catherine L; Dhaenens, Claire-Marie; Mohand-Said, Saddek; Audo, Isabelle; Sahel, Jose; Weleber, Richard G; Wilson, David J

2016-10-01

The goal of this analysis was to determine the test-retest variability of functional and structural measures from a cohort of patients with advanced forms of Stargardt Disease (STGD) participating in the SAR422459 (NCT01367444) gene therapy clinical trial. Twenty-two participants, aged 24 to 66, diagnosed with advanced forms of STGD, with at least one pathogenic ABCA4 mutation on each chromosome participating in the SAR422459 (NCT01367444) gene therapy clinical trial, were screened over three visits within 3 weeks or less. Functional visual evaluations included: best-corrected visual acuity (BCVA) Early Treatment Diabetic Retinopathy Study (ETDRS) letter score, semiautomated kinetic perimetry (SKP) using isopters I4e, III4e, and V4e, hill of vision (HOV) calculated from static visual fields (SVF) by using a 184n point centrally condensed grid with the stimulus size V test target. Retinal structural changes such as central macular thickness and macular volume were assessed by spectral-domain optical coherence tomography (SD-OCT). Repeatability coefficients (RC) and 95% confidential intervals (CI) were calculated for each parameter using a hierarchical mixed-effects model and bootstrapping. Criteria for statistically significant changes for various parameters were found to be the following: BCVA letter score (8 letters), SKP isopters I4e, III4e, and V4e (3478.85; 2488.02 and 2622.46 deg 2 , respectively), SVF full volume HOV (V TOT, 14.62 dB-sr), central macular thickness, and macular volume (4.27 μm and 0.15 mm 3 , respectively). This analysis provides important information necessary to determine if significant changes are occurring in structural and functional assessments commonly used to measure disease progression in this cohort of patients with STGD. Moreover, this information is useful for future trials assessing safety and efficacy of treatments in STGD. Determination of variability of functional and structural measures in participants with advanced stages of the STGD is necessary to assess efficacy and safety in treatment trials involving STGD patients.

Psychosocial functioning in adolescents with complex partial seizures.

PubMed

Elliott, I

1992-03-01

This pilot study examined psychosocial functioning in adolescents (age 12.5-18.5 years) with complex partial seizures. Twenty-five subjects were divided into three groups: Group I (N = 11), medically treated with uncontrolled seizures; Group II (N = 6), medically managed with controlled seizures; and Group III (N = 8), epilepsy refractory to medical management with seizure control following surgery. Psychosocial functioning was measured using the "Adolescent Psychosocial Inventory" of Batzel and Dodrill. Findings revealed significant differences (F 4.80. p less than 0.02) in psychosocial functioning between the three groups. Group I showed the poorest overall adjustment; Group II, the best adjustment; Group III was better adjusted than Group I, but less than Group II. Significant difficulties were evident in the areas of school, interpersonal, emotional, seizure adjustment and overall psychosocial functioning in Group III. No problems were evident in Group II. School, emotional and overall adjustment were moderately problematic in Group III. Analysis of biological and demographic data revealed a significant association between increased numbers of medications and poorer psychosocial functioning (r = 58, p less than 0.02). The study results provide direction for clinic and community nurse specialists to set priorities with regard to assessment and supportive interventions.

Studies in astronomical time series analysis. III - Fourier transforms, autocorrelation functions, and cross-correlation functions of unevenly spaced data

NASA Technical Reports Server (NTRS)

Scargle, Jeffrey D.

1989-01-01

This paper develops techniques to evaluate the discrete Fourier transform (DFT), the autocorrelation function (ACF), and the cross-correlation function (CCF) of time series which are not evenly sampled. The series may consist of quantized point data (e.g., yes/no processes such as photon arrival). The DFT, which can be inverted to recover the original data and the sampling, is used to compute correlation functions by means of a procedure which is effectively, but not explicitly, an interpolation. The CCF can be computed for two time series not even sampled at the same set of times. Techniques for removing the distortion of the correlation functions caused by the sampling, determining the value of a constant component to the data, and treating unequally weighted data are also discussed. FORTRAN code for the Fourier transform algorithm and numerical examples of the techniques are given.

One-year prospective replication study of an untreated sample of community dysthymia subjects.

PubMed

McCullough, J P; McCune, K J; Kaye, A L; Braith, J A; Friend, R; Roberts, W C; Belyea-Caldwell, S; Norris, S L; Hampton, C

1994-07-01

This study replicates an earlier naturalistic-prospective investigation of nontreatment, community DSM-III-R dysthymia subjects. Major goals were to determine spontaneous remission rates and monitor the stability of psychosocial functioning levels over time. Twenty-four dysthymia subjects were followed for 1 year. Three remissions (13%) were diagnosed at the final interview. At a 4-year diagnostic follow-up contact with the remitters only, one remitter had relapsed and two remained in remission. Subjects were monitored for depressive symptom intensity, personality functioning, general medical distress, cognitive functioning, coping stylistics, interpersonal functioning, quality of their social support resources, and general family functioning. Stable levels of psychosocial functioning were maintained across all measures over the 1-year period. Current psychometric findings confirm the conclusions of the earlier nontreatment prospective study that dysthymia is a chronic mood disorder with stable psychosocial features and is unlikely to remit spontaneously over time.

Subunit compositions of Arabidopsis RNA polymerases I and III reveal Pol I- and Pol III-specific forms of the AC40 subunit and alternative forms of the C53 subunit

PubMed Central

Ream, Thomas S.; Haag, Jeremy R.; Pontvianne, Frederic; Nicora, Carrie D.; Norbeck, Angela D.; Paša-Tolić, Ljiljana; Pikaard, Craig S.

2015-01-01

Using affinity purification and mass spectrometry, we identified the subunits of Arabidopsis thaliana multisubunit RNA polymerases I and III (abbreviated as Pol I and Pol III), the first analysis of their physical compositions in plants. In all eukaryotes examined to date, AC40 and AC19 subunits are common to Pol I (a.k.a. Pol A) and Pol III (a.k.a. Pol C) and are encoded by single genes. Surprisingly, A. thaliana and related species express two distinct AC40 paralogs, one of which assembles into Pol I and the other of which assembles into Pol III. Changes at eight amino acid positions correlate with the functional divergence of Pol I- and Pol III-specific AC40 paralogs. Two genes encode homologs of the yeast C53 subunit and either protein can assemble into Pol III. By contrast, only one of two potential C17 variants, and one of two potential C31 variants were detected in Pol III. We introduce a new nomenclature system for plant Pol I and Pol III subunits in which the 12 subunits that are structurally and functionally homologous among Pols I through V are assigned equivalent numbers. PMID:25813043

Hyperoxia Causes Mitochondrial Fragmentation in Pulmonary Endothelial Cells by Increasing Expression of Pro-Fission Proteins.

PubMed

Ma, Cui; Beyer, Andreas M; Durand, Matthew; Clough, Anne V; Zhu, Daling; Norwood Toro, Laura; Terashvili, Maia; Ebben, Johnathan D; Hill, R Blake; Audi, Said H; Medhora, Meetha; Jacobs, Elizabeth R

2018-03-01

We explored mechanisms that alter mitochondrial structure and function in pulmonary endothelial cells (PEC) function after hyperoxia. Mitochondrial structures of PECs exposed to hyperoxia or normoxia were visualized and mitochondrial fragmentation quantified. Expression of pro-fission or fusion proteins or autophagy-related proteins were assessed by Western blot. Mitochondrial oxidative state was determined using mito-roGFP. Tetramethylrhodamine methyl ester estimated mitochondrial polarization in treatment groups. The role of mitochondrially derived reactive oxygen species in mt-fragmentation was investigated with mito-TEMPOL and mitochondrial DNA (mtDNA) damage studied by using ENDO III (mt-tat-endonuclease III), a protein that repairs mDNA damage. Drp-1 (dynamin-related protein 1) was overexpressed or silenced to test the role of this protein in cell survival or transwell resistance. Hyperoxia increased fragmentation of PEC mitochondria in a time-dependent manner through 48 hours of exposure. Hyperoxic PECs exhibited increased phosphorylation of Drp-1 (serine 616), decreases in Mfn1 (mitofusion protein 1), but increases in OPA-1 (optic atrophy 1). Pro-autophagy proteins p62 (LC3 adapter-binding protein SQSTM1/p62), PINK-1 (PTEN-induced putative kinase 1), and LC3B (microtubule-associated protein 1A/1B-light chain 3) were increased. Returning cells to normoxia for 24 hours reversed the increased mt-fragmentation and changes in expression of pro-fission proteins. Hyperoxia-induced changes in mitochondrial structure or cell survival were mitigated by antioxidants mito-TEMPOL, Drp-1 silencing, or inhibition or protection by the mitochondrial endonuclease ENDO III. Hyperoxia induced oxidation and mitochondrial depolarization and impaired transwell resistance. Decrease in resistance was mitigated by mito-TEMPOL or ENDO III and reproduced by overexpression of Drp-1. Because hyperoxia evoked mt-fragmentation, cell survival and transwell resistance are prevented by ENDO III and mito-TEMPOL and Drp-1 silencing, and these data link hyperoxia-induced mt-DNA damage, Drp-1 expression, mt-fragmentation, and PEC dysfunction. © 2018 American Heart Association, Inc.

Metal-Assisted Oxo Atom Addition to an Fe(III) Thiolate.

PubMed

Villar-Acevedo, Gloria; Lugo-Mas, Priscilla; Blakely, Maike N; Rees, Julian A; Ganas, Abbie S; Hanada, Erin M; Kaminsky, Werner; Kovacs, Julie A

2017-01-11

Cysteinate oxygenation is intimately tied to the function of both cysteine dioxygenases (CDOs) and nitrile hydratases (NHases), and yet the mechanisms by which sulfurs are oxidized by these enzymes are unknown, in part because intermediates have yet to be observed. Herein, we report a five-coordinate bis-thiolate ligated Fe(III) complex, [Fe III (S 2 Me2 N 3 (Pr,Pr))] + (2), that reacts with oxo atom donors (PhIO, IBX-ester, and H 2 O 2 ) to afford a rare example of a singly oxygenated sulfenate, [Fe III (η 2 -S Me2 O)(S Me2 )N 3 (Pr,Pr)] + (5), resembling both a proposed intermediate in the CDO catalytic cycle and the essential NHase Fe-S(O) Cys114 proposed to be intimately involved in nitrile hydrolysis. Comparison of the reactivity of 2 with that of a more electron-rich, crystallographically characterized derivative, [Fe III S 2 Me2 N Me N 2 amide (Pr,Pr)] - (8), shows that oxo atom donor reactivity correlates with the metal ion's ability to bind exogenous ligands. Density functional theory calculations suggest that the mechanism of S-oxygenation does not proceed via direct attack at the thiolate sulfurs; the average spin-density on the thiolate sulfurs is approximately the same for 2 and 8, and Mulliken charges on the sulfurs of 8 are roughly twice those of 2, implying that 8 should be more susceptible to sulfur oxidation. Carboxamide-ligated 8 is shown to be unreactive towards oxo atom donors, in contrast to imine-ligated 2. Azide (N 3 - ) is shown to inhibit sulfur oxidation with 2, and a green intermediate is observed, which then slowly converts to sulfenate-ligated 5. This suggests that the mechanism of sulfur oxidation involves initial coordination of the oxo atom donor to the metal ion. Whether the green intermediate is an oxo atom donor adduct, Fe-O═I-Ph, or an Fe(V)═O remains to be determined.

How Do Executive Functions Fit with the Cattell-Horn-Carroll Model? Some Evidence from a Joint Factor Analysis of the Delis-Kaplan Executive Function System and the Woodcock-Johnson III Tests of Cognitive Abilities

ERIC Educational Resources Information Center

Floyd, Randy G.; Bergeron, Renee; Hamilton, Gloria; Parra, Gilbert R.

2010-01-01

This study investigated the relations among executive functions and cognitive abilities through a joint exploratory factor analysis and joint confirmatory factor analysis of 25 test scores from the Delis-Kaplan Executive Function System and the Woodcock-Johnson III Tests of Cognitive Abilities. Participants were 100 children and adolescents…

Separation and Determination of Fe(III) and Fe(II) in Natural and Waste Waters Using Silica Gel Sequentially Modified with Polyhexamethylene Guanidine and Tiron

PubMed Central

Maksimov, Nikolay; Trofimchuk, Anatoly; Zaporogets, Olga

2017-01-01

Silica gel, sequentially modified with polyhexamethylene guanidine and pyrocatechin-3,5-disulfonic acid (Tiron), was suggested for sorption separation and determination of Fe(III) and Fe(II). It was found that quantitative extraction of Fe(III) and its separation from Fe(II) were attained at pH 2.5–4.0, while quantitative extraction of Fe(II) was observed at pH 6.0–7.5. An intensive signal with g = 4.27, which is characteristic for Fe(III), appeared in EPR spectra of the sorbents after Fe(II) and Fe(III) sorption. During interaction between Fe(II) and Tiron, fixed on the sorbent surface, its oxidation up to Fe(III) occurred. Red-lilac complexes of the composition FeL3 were formed on the sorbent surface during sorption regardless of initial oxidation level of iron. Diffuse reflectance spectrum of surface complexes exhibited wide band with slightly expressed maxima at 480 and 510 nm. Procedures for separation and photometric determination of Fe(III) and Fe(II) at the joint presence and total Fe content determination as Fe(II) in waste and natural waters was developed. The limit of detection for iron was 0.05 μg per 0.100 g of the sorbent. The calibration graph was linear up to 20.0 μg of Fe per 0.100 g of the sorbent. The RSD in the determination of more than 0.2 μg of Fe was less than 0.06. PMID:29214095

A structural role for the PHP domain in E. coli DNA polymerase III.

PubMed

Barros, Tiago; Guenther, Joel; Kelch, Brian; Anaya, Jordan; Prabhakar, Arjun; O'Donnell, Mike; Kuriyan, John; Lamers, Meindert H

2013-05-14

In addition to the core catalytic machinery, bacterial replicative DNA polymerases contain a Polymerase and Histidinol Phosphatase (PHP) domain whose function is not entirely understood. The PHP domains of some bacterial replicases are active metal-dependent nucleases that may play a role in proofreading. In E. coli DNA polymerase III, however, the PHP domain has lost several metal-coordinating residues and is likely to be catalytically inactive. Genomic searches show that the loss of metal-coordinating residues in polymerase PHP domains is likely to have coevolved with the presence of a separate proofreading exonuclease that works with the polymerase. Although the E. coli Pol III PHP domain has lost metal-coordinating residues, the structure of the domain has been conserved to a remarkable degree when compared to that of metal-binding PHP domains. This is demonstrated by our ability to restore metal binding with only three point mutations, as confirmed by the metal-bound crystal structure of this mutant determined at 2.9 Å resolution. We also show that Pol III, a large multi-domain protein, unfolds cooperatively and that mutations in the degenerate metal-binding site of the PHP domain decrease the overall stability of Pol III and reduce its activity. While the presence of a PHP domain in replicative bacterial polymerases is strictly conserved, its ability to coordinate metals and to perform proofreading exonuclease activity is not, suggesting additional non-enzymatic roles for the domain. Our results show that the PHP domain is a major structural element in Pol III and its integrity modulates both the stability and activity of the polymerase.

Lenalidomide enhances the function of chimeric antigen receptor T cells against the epidermal growth factor receptor variant III by enhancing immune synapses.

PubMed

Kuramitsu, S; Ohno, M; Ohka, F; Shiina, S; Yamamichi, A; Kato, A; Tanahashi, K; Motomura, K; Kondo, G; Kurimoto, M; Senga, T; Wakabayashi, T; Natsume, A

2015-10-01

The epidermal growth factor receptor variant III (EGFRvIII) is exclusively expressed on the cell surface in ~50% of glioblastoma multiforme (GBM). This variant strongly and persistently activates the phosphatidylinositol 3-kinase-Akt signaling pathway in a ligand-independent manner resulting in enhanced tumorigenicity, cellular motility and resistance to chemoradiotherapy. Our group generated a recombinant single-chain variable fragment (scFv) antibody specific to the EGFRvIII, referred to as 3C10-scFv. In the current study, we constructed a lentiviral vector transducing the chimeric antigen receptor (CAR) that consisted of 3C10-scFv, CD3ζ, CD28 and 4-1BB (3C10-CAR). The 3C10-CAR-transduced peripheral blood mononuclear cells (PBMCs) and CD3(+) T cells specifically lysed the glioma cells that express EGFRvIII. Moreover, we demonstrated that CAR CD3(+) T cells migrated to the intracranial xenograft of GBM in the mice treated with 3C10-CAR PBMCs. An important and novel finding of our study was that a thalidomide derivative lenalidomide induced 3C10-CAR PBMC proliferation and enhanced the persistent antitumor effect of the cells in vivo. Lenalidomide also exhibited enhanced immunological synapses between the effector cells and the target cells as determined by CD11a and F-actin polymerization. Collectively, lentiviral-mediated transduction of CAR effectors targeting the EGFRvIII showed specific efficacy, and lenalidomide even intensified CAR cell therapy by enhanced formation of immunological synapses.

Synthesis and Characterization of the Actinium Aquo Ion

PubMed Central

2017-01-01

Metal aquo ions occupy central roles in all equilibria that define metal complexation in natural environments. These complexes are used to establish thermodynamic metrics (i.e., stability constants) for predicting metal binding, which are essential for defining critical parameters associated with aqueous speciation, metal chelation, in vivo transport, and so on. As such, establishing the fundamental chemistry of the actinium(III) aquo ion (Ac-aquo ion, Ac(H2O)x3+) is critical for current efforts to develop 225Ac [t1/2 = 10.0(1) d] as a targeted anticancer therapeutic agent. However, given the limited amount of actinium available for study and its high radioactivity, many aspects of actinium chemistry remain poorly defined. We overcame these challenges using the longer-lived 227Ac [t1/2 = 21.772(3) y] isotope and report the first characterization of this fundamentally important Ac-aquo coordination complex. Our X-ray absorption fine structure study revealed 10.9 ± 0.5 water molecules directly coordinated to the AcIII cation with an Ac–OH2O distance of 2.63(1) Å. This experimentally determined distance was consistent with molecular dynamics density functional theory results that showed (over the course of 8 ps) that AcIII was coordinated by 9 water molecules with Ac–OH2O distances ranging from 2.61 to 2.76 Å. The data is presented in the context of other actinide(III) and lanthanide(III) aquo ions characterized by XAFS and highlights the uniqueness of the large AcIII coordination numbers and long Ac–OH2O bond distances. PMID:28386595

Interaction of silicene with amino acid analogues—from physical to chemical adsorption in gas and solvated phases

NASA Astrophysics Data System (ADS)

Jagvaral, Yesukhei; He, Haiying; Pandey, Ravindra

2018-01-01

Silicene is an emerging 2D material, and an understanding of its interaction with amino acids, the basic building blocks of protein, is of fundamental importance. In this paper, we investigate the nature of adsorption of amino-acid analogues on silicene employing density functional theory and an implicit solvation model. Amino acid analogues are defined as CH3-R molecules, where R is the functional group of the amino acid side chain. The calculated results find three distinct groups within the amino-acid analogues considered: (i) group I, which includes MeCH3 and MeSH, interacts with silicene via the van der Waals dispersive terms leading to physisorbed configurations; (ii) group II strongly interacts with silicene forming Si-O/N chemical bonds in the chemisorbed configurations; and (iii) group III, which consists of the phenyl group, interacts with silicene via π-π interactions leading to physisorbed configurations. The results show that the lateral chains of the amino acids intrinsically determine the interactions between protein and silicene at the interface under the given physiological conditions.

Type III Nrg1 Back Signaling Enhances Functional TRPV1 along Sensory Axons Contributing to Basal and Inflammatory Thermal Pain Sensation

PubMed Central

Canetta, Sarah E.; Luca, Edlira; Pertot, Elyse; Role, Lorna W.; Talmage, David A.

2011-01-01

Type III Nrg1, a member of the Nrg1 family of signaling proteins, is expressed in sensory neurons, where it can signal in a bi-directional manner via interactions with the ErbB family of receptor tyrosine kinases (ErbB RTKs) [1]. Type III Nrg1 signaling as a receptor (Type III Nrg1 back signaling) can acutely activate phosphatidylinositol-3-kinase (PtdIns3K) signaling, as well as regulate levels of α7* nicotinic acetylcholine receptors, along sensory axons [2]. Transient receptor potential vanilloid 1 (TRPV1) is a cation-permeable ion channel found in primary sensory neurons that is necessary for the detection of thermal pain and for the development of thermal hypersensitivity to pain under inflammatory conditions [3]. Cell surface expression of TRPV1 can be enhanced by activation of PtdIns3K [4], [5], [6], making it a potential target for regulation by Type III Nrg1. We now show that Type III Nrg1 signaling in sensory neurons affects functional axonal TRPV1 in a PtdIns3K-dependent manner. Furthermore, mice heterozygous for Type III Nrg1 have specific deficits in their ability to respond to noxious thermal stimuli and to develop capsaicin-induced thermal hypersensitivity to pain. Cumulatively, these results implicate Type III Nrg1 as a novel regulator of TRPV1 and a molecular mediator of nociceptive function. PMID:21949864

Validation of Resource Utilization Groups version III for Home Care (RUG-III/HC): evidence from a Canadian home care jurisdiction.

PubMed

Poss, Jeffrey W; Hirdes, John P; Fries, Brant E; McKillop, Ian; Chase, Mary

2008-04-01

The case-mix system Resource Utilization Groups version III for Home Care (RUG-III/HC) was derived using a modest data sample from Michigan, but to date no comprehensive large scale validation has been done. This work examines the performance of the RUG-III/HC classification using a large sample from Ontario, Canada. Cost episodes over a 13-week period were aggregated from individual level client billing records and matched to assessment information collected using the Resident Assessment Instrument for Home Care, from which classification rules for RUG-III/HC are drawn. The dependent variable, service cost, was constructed using formal services plus informal care valued at approximately one-half that of a replacement worker. An analytic dataset of 29,921 episodes showed a skewed distribution with over 56% of cases falling into the lowest hierarchical level, reduced physical functions. Case-mix index values for formal and informal cost showed very close similarities to those found in the Michigan derivation. Explained variance for a function of combined formal and informal cost was 37.3% (20.5% for formal cost alone), with personal support services as well as informal care showing the strongest fit to the RUG-III/HC classification. RUG-III/HC validates well compared with the Michigan derivation work. Potential enhancements to the present classification should consider the large numbers of undifferentiated cases in the reduced physical function group, and the low explained variance for professional disciplines.

Human DNA ligase III bridges two DNA ends to promote specific intermolecular DNA end joining

PubMed Central

Kukshal, Vandna; Kim, In-Kwon; Hura, Gregory L.; Tomkinson, Alan E.; Tainer, John A.; Ellenberger, Tom

2015-01-01

Mammalian DNA ligase III (LigIII) functions in both nuclear and mitochondrial DNA metabolism. In the nucleus, LigIII has functional redundancy with DNA ligase I whereas LigIII is the only mitochondrial DNA ligase and is essential for the survival of cells dependent upon oxidative respiration. The unique LigIII zinc finger (ZnF) domain is not required for catalytic activity but senses DNA strand breaks and stimulates intermolecular ligation of two DNAs by an unknown mechanism. Consistent with this activity, LigIII acts in an alternative pathway of DNA double strand break repair that buttresses canonical non-homologous end joining (NHEJ) and is manifest in NHEJ-defective cancer cells, but how LigIII acts in joining intermolecular DNA ends versus nick ligation is unclear. To investigate how LigIII efficiently joins two DNAs, we developed a real-time, fluorescence-based assay of DNA bridging suitable for high-throughput screening. On a nicked duplex DNA substrate, the results reveal binding competition between the ZnF and the oligonucleotide/oligosaccharide-binding domain, one of three domains constituting the LigIII catalytic core. In contrast, these domains collaborate and are essential for formation of a DNA-bridging intermediate by adenylated LigIII that positions a pair of blunt-ended duplex DNAs for efficient and specific intermolecular ligation. PMID:26130724

Human DNA ligase III bridges two DNA ends to promote specific intermolecular DNA end joining.

PubMed

Kukshal, Vandna; Kim, In-Kwon; Hura, Gregory L; Tomkinson, Alan E; Tainer, John A; Ellenberger, Tom

2015-08-18

Mammalian DNA ligase III (LigIII) functions in both nuclear and mitochondrial DNA metabolism. In the nucleus, LigIII has functional redundancy with DNA ligase I whereas LigIII is the only mitochondrial DNA ligase and is essential for the survival of cells dependent upon oxidative respiration. The unique LigIII zinc finger (ZnF) domain is not required for catalytic activity but senses DNA strand breaks and stimulates intermolecular ligation of two DNAs by an unknown mechanism. Consistent with this activity, LigIII acts in an alternative pathway of DNA double strand break repair that buttresses canonical non-homologous end joining (NHEJ) and is manifest in NHEJ-defective cancer cells, but how LigIII acts in joining intermolecular DNA ends versus nick ligation is unclear. To investigate how LigIII efficiently joins two DNAs, we developed a real-time, fluorescence-based assay of DNA bridging suitable for high-throughput screening. On a nicked duplex DNA substrate, the results reveal binding competition between the ZnF and the oligonucleotide/oligosaccharide-binding domain, one of three domains constituting the LigIII catalytic core. In contrast, these domains collaborate and are essential for formation of a DNA-bridging intermediate by adenylated LigIII that positions a pair of blunt-ended duplex DNAs for efficient and specific intermolecular ligation. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

Synthesis of oxindole from acetanilide via Ir(iii)-catalyzed C-H carbenoid functionalization.

PubMed

Patel, Pitambar; Borah, Gongutri

2016-12-22

Herein we disclose the first report on the synthesis of oxindole derivatives from acetanilide via Ir(iii)-catalyzed intermolecular C-H functionalization with diazotized Meldrum's acid. A broad range of substituted anilides were found to react smoothly under the Ir(iii)-catalytic system to afford the corresponding N-protected oxindoles. The N-protecting groups, such as Ac, Bz or Piv, can be easily removed to furnish the oxindole. Various synthetic applications of the synthesized oxindole were also demonstrated.

Rhodium(III)-Catalyzed [3+2]/[5+2] Annulation of 4-Aryl 1,2,3-Triazoles with Internal Alkynes through Dual C(sp2)-H Functionalization.

PubMed

Yang, Yuan; Zhou, Ming-Bo; Ouyang, Xuan-Hui; Pi, Rui; Song, Ren-Jie; Li, Jin-Heng

2015-05-26

A rhodium(III)-catalyzed [3+2]/[5+2] annulation of 4-aryl 1-tosyl-1,2,3-triazoles with internal alkynes is presented. This transformation provides straightforward access to indeno[1,7-cd]azepine architectures through a sequence involving the formation of a rhodium(III) azavinyl carbene, dual C(sp(2))-H functionalization, and [3+2]/[5+2] annulation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Psychological problems and family functioning as risk factors in addiction.

PubMed

Agha, Sajida; Zia, Hamid; Irfan, Syed

2008-01-01

The purpose of the present research was to determine the role of family functioning and psychological problems of drug addicts and non addicts by assessing the difference between the two groups. After detailed literature review it was hypothesized that scores on the variable of communication, affective expression and control among family members of addicts will be higher than non addicts. Furthermore scores on the variables of anger control problems, emotional distress and positive self will also be higher of addicts. This was a cohort study. A cluster sampling method was used. Sample of present research consisted of 240 adolescents divided into two groups of 120 addicts and 120 non-addicts each from different socio-economic status. General scale of Family Assessment Measure-Version III (FAM-III) was administered in order to measure the level of communication, value and norms whereas dyadic Relationship Scale was used to measure affective expression and control among the family members of addicts and non addicts. Renold Adolescent Adjustment Screening Inventory was administered in order to assess anger control problems, emotional distress and positive self in addicts and non addicts. t-test was calculated in order to determine the difference in the level of communication, value and norms, affective expression and control among families of addicts and non addicts. Furthermore difference in anger control problems, emotional distress and positive self between the addicts and non addicts was also determined by calculating t-test. Results showed significant differences in the variables among the family members and there is also a significant difference between addicts and non addicts. Avenues for further research have been suggested.

Effects of severity of gross motor disability on anticipatory postural adjustments while standing in individuals with bilateral spastic cerebral palsy.

PubMed

Tomita, Hidehito; Fukaya, Yoshiki; Takagi, Yukina; Yokozawa, Asami

2016-10-01

Although individuals with bilateral spastic cerebral palsy (BSCP) exhibit several deficits in anticipatory postural adjustments (APAs) while standing, effects of severity of motor disability on their APAs are unclear. To determine whether individuals with BSCP exhibit severity-dependent deficits in APAs. Seven individuals with level II BSCP (BSCP-II group) and seven with level III BSCP (BSCP-III group) according to the Gross Motor Function Classification System and seven healthy controls lifted a load under two different load conditions. Anticipatory activities of the erector spinae (ES), medial hamstring (MH), and gastrocnemius (GCM) were smaller in the two BSCP groups than in the control group. Although the anticipatory GCM activity was similar between the BSCP groups, the ES and MH activities were larger in the BSCP-II group than in the BSCP-III group. In the BSCP-II group, an increase in anticipatory activity with an increase in load was observed in the MH, but not in the GCM. In the BSCP-III group, load-related modulation was not found in the MH or GCM. The present findings suggest that in individuals with BSCP with severe motor disability, APA deficits extend to more proximal parts of the body. Copyright © 2016 Elsevier Ltd. All rights reserved.

Kinetics and thermodynamics of irreversible inhibition of matrix metalloproteinase 2 by a Co(III) Schiff base complex

PubMed Central

Harney, Allison S.; Sole, Laura B.

2012-01-01

Cobalt(III) Schiff base complexes have been used as potent inhibitors of protein function through the coordination to histidine residues essential for activity. The kinetics and thermodynamics of the binding mechanism of Co(acacen)(NH3)2Cl [Co(acacen); where H2acacen is bis(acetylacetone)ethylenediimine] enzyme inhibition has been examined through the inactivation of matrix metalloproteinase 2 (MMP-2) protease activity. Co(acacen) is an irreversible inhibitor that exhibits time- and concentration-dependent inactivation of MMP-2. Co(acacen) inhibition of MMP-2 is temperature-dependent, with the inactivation increasing with temperature. Examination of the formation of the transition state for the MMP-2/Co(acacen) complex was determined to have a positive entropy component indicative of greater disorder in the MMP-2/Co(acacen) complex than in the reactants. With further insight into the mechanism of Co(acacen) complexes, Co(III) Schiff base complex protein inactivators can be designed to include features regulating activity and protein specificity. This approach is widely applicable to protein targets that have been identified to have clinical significance, including matrix metalloproteinases. The mechanistic information elucidated here further emphasizes the versatility and utility of Co(III) Schiff base complexes as customizable protein inhibitors. PMID:22729838

Experimental determination of water activity for binary aqueous cerium(III) ionic solutions: application to an assessment of the predictive capability of the binding mean spherical approximation model.

PubMed

Ruas, Alexandre; Simonin, Jean-Pierre; Turq, Pierre; Moisy, Philippe

2005-12-08

This work is aimed at a description of the thermodynamic properties of actinide salt solutions at high concentration. The predictive capability of the binding mean spherical approximation (BIMSA) theory to describe the thermodynamic properties of electrolytes is assessed in the case of aqueous solutions of lanthanide(III) nitrate and chloride salts. Osmotic coefficients of cerium(III) nitrate and chloride were calculated from other lanthanide(III) salts properties. In parallel, concentrated binary solutions of cerium nitrate were prepared in order to measure experimentally its water activity and density as a function of concentration, at 25 degrees C. Water activities of several binary solutions of cerium chloride were also measured to check existing data on this salt. Then, the properties of cerium chloride and cerium nitrate solutions were compared within the BIMSA model. Osmotic coefficient values for promethium nitrate and promethium chloride given by this theory are proposed. Finally, water activity measurements were made to examine the fact that the ternary system Ce(NO3)3/HNO3/H2O and the quaternary system Ce(NO3)3/HNO3/N2H5NO3/H2O may be regarded as "simple solutions" (in the sense of Zdanovskii and Mikulin).

Determination of thallium at ultra-trace levels in water and biological samples using solid phase spectrophotometry

NASA Astrophysics Data System (ADS)

Amin, Alaa S.; El-Sharjawy, Abdel-Azeem M.; Kassem, Mohammed A.

2013-06-01

A new simple, very sensitive, selective and accurate procedure for the determination of trace amounts of thallium(III) by solid-phase spectrophotometry (SPS) has been developed. The procedure is based on fixation of Tl(III) as quinalizarin ion associate on a styrene-divinylbenzene anion-exchange resin. The absorbance of resin sorbed Tl(III) ion associate is measured directly at 636 and 830 nm. Thallium(I) was determined by difference measurements after oxidation of Tl(I) to Tl(III) with bromine. Calibration is linear over the range 0.5-12.0 μg L-1 of Tl(III) with relative standard deviation (RSD) of 1.40% (n = 10). The detection and quantification limits are 150 and 495 ng L-1 using 0.6 g of the exchanger. The molar absorptivity and Sandell sensitivity are also calculated and found to be 1.31 × 107 L mol-1 cm-1 and 0.00156 ng cm-2, respectively. The proposed procedure has been successfully applied to determine thallium in water, urine and serum samples.

Determination of thallium at ultra-trace levels in water and biological samples using solid phase spectrophotometry.

PubMed

Amin, Alaa S; El-Sharjawy, Abdel-Azeem M; Kassem, Mohammed A

2013-06-01

A new simple, very sensitive, selective and accurate procedure for the determination of trace amounts of thallium(III) by solid-phase spectrophotometry (SPS) has been developed. The procedure is based on fixation of Tl(III) as quinalizarin ion associate on a styrene-divinylbenzene anion-exchange resin. The absorbance of resin sorbed Tl(III) ion associate is measured directly at 636 and 830 nm. Thallium(I) was determined by difference measurements after oxidation of Tl(I) to Tl(III) with bromine. Calibration is linear over the range 0.5-12.0 μg L(-1) of Tl(III) with relative standard deviation (RSD) of 1.40% (n=10). The detection and quantification limits are 150 and 495 ng L(-1) using 0.6 g of the exchanger. The molar absorptivity and Sandell sensitivity are also calculated and found to be 1.31×10(7) L mol(-1)cm(-1) and 0.00156 ng cm(-2), respectively. The proposed procedure has been successfully applied to determine thallium in water, urine and serum samples. Copyright © 2013 Elsevier B.V. All rights reserved.

SMN transcript levels in leukocytes of SMA patients determined by absolute real-time PCR

PubMed Central

Tiziano, Francesco Danilo; Pinto, Anna Maria; Fiori, Stefania; Lomastro, Rosa; Messina, Sonia; Bruno, Claudio; Pini, Antonella; Pane, Marika; D'Amico, Adele; Ghezzo, Alessandro; Bertini, Enrico; Mercuri, Eugenio; Neri, Giovanni; Brahe, Christina

2010-01-01

Spinal muscular atrophy (SMA) is an autosomal recessive neuromuscular disorder caused by homozygous mutations of the SMN1 gene. Three forms of SMA are recognized (type I–III) on the basis of clinical severity. All patients have at least one or more (usually 2–4) copies of a highly homologous gene (SMN2), which produces insufficient levels of functional SMN protein, because of alternative splicing of exon 7. Recently, evidence has been provided that SMN2 expression can be enhanced by pharmacological treatment. However, no reliable biomarkers are available to test the molecular efficacy of the treatments. At present, the only potential biomarker is the dosage of SMN products in peripheral blood. However, the demonstration that SMN full-length (SMN-fl) transcript levels are reduced in leukocytes of patients compared with controls remains elusive (except for type I). We have developed a novel assay based on absolute real-time PCR, which allows the quantification of SMN1-fl/SMN2-fl transcripts. For the first time, we have shown that SMN-fl levels are reduced in leukocytes of type II–III patients compared with controls. We also found that transcript levels are related to clinical severity as in type III patients SMN2-fl levels are significantly higher compared with type II and directly correlated with functional ability in type II patients and with age of onset in type III patients. Moreover, in haploidentical siblings with discordant phenotype, the less severely affected individuals showed significantly higher transcript levels. Our study shows that SMN2-fl dosage in leukocytes can be considered a reliable biomarker and can provide the rationale for SMN dosage in clinical trials. PMID:19603064

The MRI-measured arterial input function resulting from a bolus injection of Gd-DTPA in a rat model of stroke slightly underestimates that of Gd-[14C]DTPA and marginally overestimates the blood-to-brain influx rate constant determined by Patlak plots

PubMed Central

Nagaraja, Tavarekere N.; Karki, Kishor; Ewing, James R.; Divine, George W.; Fenstermacher, Joseph D.; Patlak, Clifford S.; Knight, Robert A.

2009-01-01

The hypothesis that the arterial input function (AIF) of gadolinium-diethylenetriaminepentaacetic acid (Gd-DTPA) injected by intravenous (iv) bolus and measured by the change in the T1-relaxation rate (ΔR1; R1=1/T1) of superior sagittal sinus blood (AIF-I) approximates the AIF of 14C-labeled Gd-DTPA measured in arterial blood (AIF*) was tested in a rat stroke model (n=13). Contrary to the hypothesis, the initial part of the ΔR1-time curve was underestimated, and the area under the normalized curve for AIF-I was about 15% lower than that for AIF*, the reference AIF. Hypothetical AIF’s for Gd-DTPA (AIF-II) were derived from the AIF* values and averaged to obtain AIF-III. Influx rate constants (Ki) and proton distribution volumes at zero time (Vp+Vo) were estimated with Patlak plots of AIF-I, -II and -III and tissue ΔR1 data. For the regions of interest, the Ki’s estimated with AIF-I were slightly but not significantly higher than those obtained with AIF-II and AIF-III. In contrast, Vp+Vo was significantly higher when calculated with AIF-I. Similar estimates of Ki and Vp+Vo were obtained with AIF-II and AIF-III. In summary, AIF-I underestimated the reference AIF (AIF*); this shortcoming had little effect on the Ki calculated by Patlak plot but produced a significant overestimation of Vp+Vo. PMID:20512853

Greater understanding of normal hip physical function may guide clinicians in providing targeted rehabilitation programmes.

PubMed

Kemp, Joanne L; Schache, Anthony G; Makdissi, Michael; Sims, Kevin J; Crossley, Kay M

2013-07-01

This study investigated tests of hip muscle strength and functional performance. The specific objectives were to: (i) establish intra- and inter-rater reliability; (ii) compare differences between dominant and non-dominant limbs; (iii) compare agonist and antagonist muscle strength ratios; (iv) compare differences between genders; and (v) examine relationships between hip muscle strength, baseline measures and functional performance. Reliability study and cross-sectional analysis of hip strength and functional performance. In healthy adults aged 18-50years, normalised hip muscle peak torque and functional performance were evaluated to: (i) establish intra-rater and inter-rater reliability; (ii) analyse differences between limbs, between antagonistic muscle groups and genders; and (iii) associations between strength and functional performance. Excellent reliability (intra-rater ICC=0.77-0.96; inter-rater ICC=0.82-0.95) was observed. No difference existed between dominant and non-dominant limbs. Differences in strength existed between antagonistic pairs of muscles: hip abduction was greater than adduction (p<0.001) and hip ER was greater than IR (p<0.001). Men had greater ER strength (p=0.006) and hop for distance (p<0.001) than women. Strong associations were observed between measures of hip muscle strength (except hip flexion) and age, height, and functional performance. Deficits in hip muscle strength or functional performance may influence hip pain. In order to provide targeted rehabilitation programmes to address patient-specific impairments, and determine when individuals are ready to return to physical activity, clinicians are increasingly utilising tests of hip strength and functional performance. This study provides a battery of reliable, clinically applicable tests which can be used for these purposes. Copyright © 2012 Sports Medicine Australia. Published by Elsevier Ltd. All rights reserved.

Spectrophotometric study of the thorium-morin mixed-color system

USGS Publications Warehouse

Fletcher, M.H.; Milkey, R.G.

1956-01-01

A spectrophotometric study was made of the thoriummorin reaction to evaluate the suitability of morin as a reagent for the determination of trace amounts of thorium. At pH 2, the equilibrium constant for the reaction is 1 ?? 106, and a single complex having a thorium-morin ratio of 1 to 2 is formed. The complex shows maximum absorbance at a wave length of 410 m??, and its absorbance obeys Beer's law. The absorbance readings are highly reproducible, and the sensitivity is relatively high, an absorbance difference of 0.001 being equivalent to 0.007 ?? of ThO2 per sq. cm. The effects of acid, alcohol, and morin concentration, time, temperature, and age of the morin reagent as well as the behavior of morin with zirconium(IV), iron(III), aluminum(III), ytterbium(III), yttrium(III), uranium(VI), praseodymium(III), lead(II), lanthanum(III), and calcium(II) ions are discussed. A method is presented for the determination of thorium in pure solutions. Appropriate separations for the isolation of thorium may extend the usefulness of the method and permit the determination of trace amounts of thorium in complex materials.

Comparative developmental analysis of Drosophila and Tribolium reveals conserved and diverged roles of abrupt in insect wing evolution.

PubMed

Ravisankar, Padmapriyadarshini; Lai, Yi-Ting; Sambrani, Nagraj; Tomoyasu, Yoshinori

2016-01-15

Morphological innovation is a fundamental process in evolution, yet its molecular basis is still elusive. Acquisition of elytra, highly modified beetle forewings, is an important innovation that has driven the successful radiation of beetles. Our RNAi screening for candidate genes has identified abrupt (ab) as a potential key player in elytron evolution. In this study, we performed a series of RNA interference (RNAi) experiments in both Tribolium and Drosophila to understand the contributions of ab to the evolution of beetle elytra. We found that (i) ab is essential for proper wing vein patterning both in Tribolium and Drosophila, (ii) ab has gained a novel function in determining the unique elytron shape in the beetle lineage, (iii) unlike Hippo and Insulin, other shape determining pathways, the shape determining function of ab is specific to the elytron and not required in the hindwing, (iv) ab has a previously undescribed role in the Notch signal-associated wing formation processes, which appears to be conserved between beetles and flies. These data suggest that ab has gained a new function during elytron evolution in beetles without compromising the conserved wing-related functions. Gaining a new function without losing evolutionarily conserved functions may be a key theme in the evolution of morphologically novel structures. Copyright © 2015 Elsevier Inc. All rights reserved.

[Determination of trivalent chromium and hexavalent chromium in dried edible fungi by microwave ashing-liquid chromatography with inductively coupled plasma mass spectrometry].

PubMed

Ni, Zhanglin; Tang, Fubin; Qu, Minghua; Mo, Runhong

2014-02-01

An analytical method using liquid chromatography with inductively coupled plasma mass spectrometry (LC-ICP-MS) for the determination of trivalent chromium (Cr(III)) and hexavalent chromium (Cr(VI)) in dried edible fungi was established. Edible fungi sample was ashed by a microwave ashing system and Na2 EDTA was added to the ashing sample to stabilize the Cr(III). An anion exchange column (250 mm x 4.6 mm, 10 microm) with a 60 mmol/L nitric acid (pH 9.3) solution as mobile phase was used for the separation and using ICP-MS as a detector for the determination of trivalent chromium and hexavalent chromium. The calibration curves were linear in the range of 0.5-50 microg/L and the correlation coefficients were 0. 999 9 for Cr(III) and Cr(VI). The average recoveries of Cr(III) and Cr(VI) ranged from 78.0% to 90.7% with the relative standard deviations (RSDs, n = 6) less than 4%. The limits of quantification (LOQ) of Cr(III) and Cr(VI) were 0.5 microg/L. The method is efficient, reliable and sensitive, and can meet the requirement for the determination of Cr(III) and Cr(VI) in dried edible fungi.

Chemical Approaches for Structure and Function of RNA in Postgenomic Era

PubMed Central

Ro-Choi, Tae Suk; Choi, Yong Chun

2012-01-01

In the study of cellular RNA chemistry, a major thrust of research focused upon sequence determinations for decades. Structures of snRNAs (4.5S RNA I (Alu), U1, U2, U3, U4, U5, and U6) were determined at Baylor College of Medicine, Houston, Tex, in an earlier time of pregenomic era. They show novel modifications including base methylation, sugar methylation, 5′-cap structures (types 0–III) and sequence heterogeneity. This work offered an exciting problem of posttranscriptional modification and underwent numerous significant advances through technological revolutions during pregenomic, genomic, and postgenomic eras. Presently, snRNA research is making progresses involved in enzymology of snRNA modifications, molecular evolution, mechanism of spliceosome assembly, chemical mechanism of intron removal, high-order structure of snRNA in spliceosome, and pathology of splicing. These works are destined to reach final pathway of work “Function and Structure of Spliceosome” in addition to exciting new exploitation of other noncoding RNAs in all aspects of regulatory functions. PMID:22347623

The critical boundary RSOS M(3,5) model

NASA Astrophysics Data System (ADS)

El Deeb, O.

2017-12-01

We consider the critical nonunitary minimal model M(3, 5) with integrable boundaries and analyze the patterns of zeros of the eigenvalues of the transfer matrix and then determine the spectrum of the critical theory using the thermodynamic Bethe ansatz ( TBA) equations. Solving the TBA functional equation satisfied by the transfer matrices of the associated A 4 restricted solid-on-solid Forrester-Baxter lattice model in regime III in the continuum scaling limit, we derive the integral TBA equations for all excitations in the ( r, s) = (1, 1) sector and then determine their corresponding energies. We classify the excitations in terms of ( m, n) systems.

Dynamic Leading-Edge Stagnation Point Determination Utilizing an Array of Hot-Film Sensors with Unknown Calibration

NASA Technical Reports Server (NTRS)

Ellsworth, Joel C.

2017-01-01

During flight-testing of the National Aeronautics and Space Administration (NASA) Gulfstream III (G-III) airplane (Gulfstream Aerospace Corporation, Savannah, Georgia) SubsoniC Research Aircraft Testbed (SCRAT) between March 2013 and April 2015 it became evident that the sensor array used for stagnation point detection was not functioning as expected. The stagnation point detection system is a self calibrating hot-film array; the calibration was unknown and varied between flights, however, the channel with the lowest power consumption was expected to correspond with the point of least surface shear. While individual channels showed the expected behavior for the hot-film sensors, more often than not the lowest power consumption occurred at a single sensor (despite in-flight maneuvering) in the array located far from the expected stagnation point. An algorithm was developed to process the available system output and determine the stagnation point location. After multiple updates and refinements, the final algorithm was not sensitive to the failure of a single sensor in the array, but adjacent failures beneath the stagnation point crippled the algorithm.

Critical Behaviors in Contagion Dynamics.

PubMed

Böttcher, L; Nagler, J; Herrmann, H J

2017-02-24

We study the critical behavior of a general contagion model where nodes are either active (e.g., with opinion A, or functioning) or inactive (e.g., with opinion B, or damaged). The transitions between these two states are determined by (i) spontaneous transitions independent of the neighborhood, (ii) transitions induced by neighboring nodes, and (iii) spontaneous reverse transitions. The resulting dynamics is extremely rich including limit cycles and random phase switching. We derive a unifying mean-field theory. Specifically, we analytically show that the critical behavior of systems whose dynamics is governed by processes (i)-(iii) can only exhibit three distinct regimes: (a) uncorrelated spontaneous transition dynamics, (b) contact process dynamics, and (c) cusp catastrophes. This ends a long-standing debate on the universality classes of complex contagion dynamics in mean field and substantially deepens its mathematical understanding.

The origin of phosphorescence in Iridium (III) complexes. The role of relativistic effects

NASA Astrophysics Data System (ADS)

Cantero-López, Plinio; Páez-Hernández, Dayan; Arratia-Pérez, Ramiro

2017-10-01

A series of luminescent Ir(III) complexes of the type [Ir(F2ppy)2L] (where L = Lpytz , LOMe , Lbut) have been studied using relativistic two-component density functional theory considering the spin-orbit coupling. The absorption spectra of the three complexes were determined. The most important transition appears in the region between 250 and 350 nm, which is in good agreement with the experimental reports. The three complexes show phosphorescent properties due to a metal-ligand charge transfer (MLCT) process, where the spin-orbit coupling (SOC) plays a key role due to the introduction of a zero field splitting (ZFS) and the mixing of states with different spins which contributes to modify the emission selection rule. The lifetimes of the emission processes were calculated, and the values are in the same order of the experimental reports.

76 FR 71450 - Approval and Promulgation of Air Quality Implementation Plans; West Virginia; Determination of...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-11-18

..., Region III, 1650 Arch Street, Philadelphia, Pennsylvania 19103. FOR FURTHER INFORMATION CONTACT: Asrah... EPA taking? II. What is the effect of this action? III. Statutory and Executive Order Reviews I. What... discussion of the rationale behind this determination and the effect of the determination were included in...

Sensitized spectrophotometric determination of Cr(III) ion for speciation of chromium ion in surfactant media using alpha-benzoin oxime.

PubMed

Ghaedi, Mehrorang; Asadpour, Enayat; Vafaie, Azam

2006-01-01

A simple and accurate micellanized spectrophotometric method for determination of trace amounts of Cr(III) ion in tab and top water and a synthetic mixture has been described. The micellar method is based on effect of organized molecular assemblies such as micelles in spectrophotometric measurement due to their effect on the systems of interest. The ability of micellar system in solubilizing of sparingly soluble ligand or complexes has been used for increasing figures of merit of an analytical method. Due to solubility increasing in aqueous media requirement for a primary extraction can be eliminated. Using the alpha-benzoin oxime (alpha-BO) spectrophotometric determination of Cr(III) ion has been performed and results are compared. The spectrophotometric determination of Cr(III) ion using alpha-BO in the presence of non-ionic surfactant Triton X-100 has been performed. The influence of type and amount of surfactant, pH, complexation time and amount of ligand were examined. Finally, the repeatability, accuracy and the effect of interfering ions on the determination of Cr(III) ion was evaluated. The proposed methods successfully with recovery yield of almost 100% have been applied to the rapid and simple determination of Cr(III) ion in the real samples. There is a good agreement between methods and atomic absorption spectrometry. The Beers law is obeyed over the concentration range of 0.1-13.7 microg mL(-1) for micellar media. The detection limit is 0.8 ng mL(-1). The molar absorptivity of complex is 5350 L mol(-1) cm(-1).

Sensitized spectrophotometric determination of Cr(III) ion for speciation of chromium ion in surfactant media using α-benzoin oxime

NASA Astrophysics Data System (ADS)

Ghaedi, Mehrorang; Asadpour, Enayat; Vafaie, Azam

2006-01-01

A simple and accurate micellanized spectrophotometric method for determination of trace amounts of Cr(III) ion in tab and top water and a synthetic mixture has been described. The micellar method is based on effect of organized molecular assemblies such as micelles in spectrophotometric measurement due to their effect on the systems of interest. The ability of micellar system in solubilizing of sparingly soluble ligand or complexes has been used for increasing figures of merit of an analytical method. Due to solubility increasing in aqueous media requirement for a primary extraction can be eliminated. Using the α-benzoin oxime (α-BO) spectrophotometric determination of Cr(III) ion has been performed and results are compared. The spectrophotometric determination of Cr(III) ion using α-BO in the presence of non-ionic surfactant Triton X-100 has been performed. The influence of type and amount of surfactant, pH, complexation time and amount of ligand were examined. Finally, the repeatability, accuracy and the effect of interfering ions on the determination of Cr(III) ion was evaluated. The proposed methods successfully with recovery yield of almost 100% have been applied to the rapid and simple determination of Cr(III) ion in the real samples. There is a good agreement between methods and atomic absorption spectrometry. The Beers law is obeyed over the concentration range of 0.1-13.7 μg mL-1 for micellar media. The detection limit is 0.8 ng mL-1. The molar absorptivity of complex is 5350 L mol-1 cm-1.

Tracing the first stars and galaxies of the Milky Way

NASA Astrophysics Data System (ADS)

Griffen, Brendan F.; Dooley, Gregory A.; Ji, Alexander P.; O'Shea, Brian W.; Gómez, Facundo A.; Frebel, Anna

2018-02-01

We use 30 high-resolution dark matter haloes of the Caterpillar simulation suite to probe the first stars and galaxies of Milky Way-mass systems. We quantify the environment of the high-z progenitors of the Milky Way and connect them to the properties of the host and satellites today. We identify the formation sites of the first generation of Population III (Pop III) stars (z ˜ 25) and first galaxies (z ˜ 22) with several different models based on a minimum halo mass. This includes a simple model for radiative feedback, the primary limitation of the model. Through this method we find approximately 23 000 ± 5000 Pop III potentially star-forming sites per Milky Way-mass host, though this number is drastically reduced to ˜550 star-forming sites if feedback is included. The majority of these haloes identified form in isolation (96 per cent at z = 15) and are not subject to external enrichment by neighbouring haloes (median separation ˜1 kpc at z = 15), though half merge with a system larger than themselves within 1.5 Gyr. Using particle tagging, we additionally trace the Pop III remnant population to z = 0 and find an order of magnitude scatter in their number density at small (i.e. r < 5 kpc) and large (i.e. r > 50 kpc) galactocentric radii. We provide fitting functions for determining the number of progenitor minihalo and atomic cooling halo systems that present-day satellite galaxies might have accreted since their formation. We determine that observed dwarf galaxies with stellar masses below 104.6 M⊙ are unlikely to have merged with any other star-forming systems.

Recipient age as a determinant factor of patient and graft survival.

PubMed

Moreso, Francesc; Ortega, Francisco; Mendiluce, Alicia

2004-06-01

Age of renal transplants has been related to death, alloimmune response and graft outcome. We reviewed the influence of patient age on transplant outcome in three cohorts of patients transplanted in Spain during the 1990 s. Patient age was categorized into four groups (I, 18-40; II, 41-50; III, 51-60; and IV, > 60 years). Risks factors for acute rejection were evaluated by logistic regression adjusting for transplant centre and transplantation year, while a Cox proportional hazard model was employed for analysing patient and graft survival. Older patients had a higher death rate (I, 3.5%; II, 7.7%; III, 13.2%; and IV, 16.9%; P<0.001), but a lower standardized mortality index (I, 7.6; II, 7.0; III, 5.8; and IV, 4.1; P = 0.0019). Older patients had the lowest risk of acute rejection [odds ratio (OR) 0.79 and 95% confidence interval (CI) 0.66-0.97 for group II; OR 0.75 and 95% CI 0.62-0.91 for group III; OR 0.43 and 95% CI 0.33-0.56 for group IV). Death-censored graft survival was poorer in patients older than 60 years (relative risk 1.40; 95% CI 1.09-1.80), but this result was not explained by any combination of patient age with donor age, delayed graft function or immunosuppression. Patient age is a main determinant of transplant outcome. Although death rate is higher for older patients, standardized mortality was not. Thus, the efforts to reduce mortality should be also implemented in younger patients. Old patients have a low risk of acute rejection but a poorer death-censored graft survival. This last result was not explained by any controlled variable in our study.

Chemical functionalization of diatom silica microparticles for adsorption of gold (III) ions.

PubMed

Yu, Yang; Addai-Mensah, Jonas; Losic, Dusan

2011-12-01

Diatom silica microparticles from natural diatomaceous earth (DE) silica have been functionalized with 3-mercaptopropyltrimethoxysilane (MPTMS) and their application for adsorption of gold (III) ions from aqueous solutions is demonstrated. Fourier transform infrared spectroscopy (FTIR) and X-ray Photoelectron spectroscopy (XPS) analyses of the MPTMS modified diatom microparticles revealed that the silane layer with functional group (-SH) was successfully introduced to the diatom surface. The adsorption study of Au(III) ions using MPTMS-DE indicated that the process depends on initial gold (III) concentration and pH showing maximum adsorption capacity at pH = 3. The Au(III) adsorption kinetics results showed that the adsorption was very fast and followed a pseudo-second-order reaction model. The Langmuir model was used to provide a sound mechanistic basis for the theoretical of the adsorption equilibrium data. Gold recovery from MPTMS-DE structures was also investigated by using acidified thiourea solution and found to be high (> 95%). These results show that chemically modified DE microparticles can be used as a new, cost effective and environmentally benign adsorbent suitable for adsorption of gold metal ions from aqueous solutions.

New Onset of Constipation during Long-Term Physical Inactivity: A Proof-of-Concept Study on the Immobility-Induced Bowel Changes

PubMed Central

Iovino, Paola; Chiarioni, Giuseppe; Bilancio, Giancarlo; Cirillo, Massimo; Mekjavic, Igor B.; Pisot, Rado; Ciacci, Carolina

2013-01-01

Background The pathophysiological mechanisms underlining constipation are incompletely understood, but prolonged bed rest is commonly considered a relevant determinant. Aims Our primary aim was to study the effect of long-term physical inactivity on determining a new onset of constipation. Secondary aim were the evaluation of changes in stool frequency, bowel function and symptoms induced by this prolonged physical inactivity. Methods Ten healthy men underwent a 7-day run-in followed by 35-day study of experimentally-controlled bed rest. The study was sponsored by the Italian Space Agency. The onset of constipation was evaluated according to Rome III criteria for functional constipation. Abdominal bloating, flatulence, pain and urgency were assessed by a 100mm Visual Analog Scales and bowel function by adjectival scales (Bristol Stool Form Scale, ease of passage of stool and sense of incomplete evacuation). Daily measurements of bowel movements was summarized on a weekly score. Pre and post bed rest Quality of Life (SF-36), general health (Goldberg’s General Health) and depression mood (Zung scale) questionnaires were administered. Results New onset of functional constipation fulfilling Rome III criteria was found in 60% (6/10) of participants (p=0.03). The score of flatulence significantly increased whilst the stool frequency significantly decreased during the week-by-week comparisons period (repeated-measures ANOVA, p=0.02 and p=0.001, respectively). Stool consistency and bowel symptoms were not influenced by prolonged physical inactivity. In addition, no significant changes were observed in general health, in mood state and in quality of life at the end of bed rest Conclusions Our results provide evidence that prolonged physical inactivity is relevant etiology in functional constipation in healthy individuals. The common clinical suggestion of early mobilization in bedridden patients is supported as well. PMID:23977327

CF3 Derivatives of the Anticancer Ru(III) Complexes KP1019, NKP-1339, and Their Imidazole and Pyridine Analogues Show Enhanced Lipophilicity, Albumin Interactions, and Cytotoxicity.

PubMed

Chang, Stephanie W; Lewis, Andrew R; Prosser, Kathleen E; Thompson, John R; Gladkikh, Margarita; Bally, Marcel B; Warren, Jeffrey J; Walsby, Charles J

2016-05-16

The Ru(III) complexes indazolium [trans-RuCl4(1H-indazole)2] (KP1019) and sodium [trans-RuCl4(1H-indazole)2] (NKP-1339) are leading candidates for the next generation of metal-based chemotherapeutics. Trifluoromethyl derivatives of these compounds and their imidazole and pyridine analogues were synthesized to probe the effect of ligand lipophilicity on the pharmacological properties of these types of complexes. Addition of CF3 groups also provided a spectroscopic handle for (19)F NMR studies of ligand exchange processes and protein interactions. The lipophilicities of the CF3-functionalized compounds and their unsubstituted parent complexes were quantified by the shake-flask method to give the distribution coefficient D at pH 7.4 (log D7.4). The solution behavior of the CF3-functionalized complexes was characterized in phosphate-buffered saline (PBS) using (19)F NMR, electron paramagnetic resonance (EPR), and UV-vis spectroscopies. These techniques, along with fluorescence competition experiments, were also used to characterize interactions with human serum albumin (HSA). From these studies it was determined that increased lipophilicity correlates with reduced solubility in PBS but enhancement of noncoordinate interactions with hydrophobic domains of HSA. These protein interactions improve the solubility of the complexes and inhibit the formation of oligomeric species. EPR measurements also demonstrated the formation of HSA-coordinated species with longer incubation. (19)F NMR spectra show that the trifluoromethyl complexes release axial ligands in PBS and in the presence of HSA. In vitro testing showed that the most lipophilic complexes had the greatest cytotoxic activity. Addition of CF3 groups enhances the activity of the indazole complex against A549 nonsmall cell lung carcinoma cells. Furthermore, in the case of the pyridine complexes, the parent compound was inactive against the HT-29 human colon carcinoma cell line but showed strong cytotoxicity with CF3 functionalization. Overall, these studies demonstrate that lipophilicity may be a determining factor in the anticancer activity and pharmacological behavior of these types of Ru(III) complexes.

Identification and cloning of class II and III chitinases from alkaline floral nectar of Rhododendron irroratum, Ericaceae.

PubMed

Zha, Hong-Guang; Milne, Richard I; Zhou, Hong-Xia; Chen, Xiang-Yang; Sun, Hang

2016-10-01

Class II and III chitinases belonging to different glycoside hydrolase families were major nectarins in Rhododendron irroratum floral nectar which showed significant chitinolytic activity. Previous studies have demonstrated antimicrobial activity in plant floral nectar, but the molecular basis for the mechanism is still poorly understood. Two chitinases, class II (Rhchi2) and III (Rhchi3), were characterized from alkaline Rhododendron irroratum nectar by both SDS-PAGE and mass spectrometry. Rhchi2 (27 kDa) and Rhchi3 (29 kDa) are glycoside hydrolases (family 19 and 18) with theoretical pI of 8.19 and 7.04. The expression patterns of Rhchi2 and Rhchi3 were analyzed by semi-quantitative RT-PCR. Rhchi2 is expressed in flowers (corolla nectar pouches) and leaves while Rhchi3 is expressed in flowers. Chitinase in concentrated protein and fresh nectar samples was visualised by SDS-PAGE and chitinolytic activity in fresh nectar was determined spectrophotometrically via chitin-azure. Full length gene sequences were cloned with Tail-PCR and RACE. The amino acid sequence deduced from the coding region for these proteins showed high identity with known chitinases and predicted to be located in extracellular space. Fresh R. irroratum floral nectar showed significant chitinolytic activity. Our results demonstrate that class III chitinase (GH 18 family) also exists in floral nectar. The functional relationship between class II and III chitinases and the role of these pathogenesis-related proteins in antimicrobial activity in nectar is suggested.

Eu(III) sorption to TiO2 (anatase and rutile): batch, XPS, and EXAFS studies.

PubMed

Tan, Xiaoli; Fan, Qiaohui; Wang, Xiangke; Grambow, Bernd

2009-05-01

The sorption of Eu(III) on anatase and rutile was studied as a function of ionic strength, humic acid (HA, 7.5 mg/L), and electrolyte anions over a large range of pH (2-12). The presence of HA significantly affected Eu(III) sorption to anatase and rutile. The sorption of Eu(III) on anatase and rutile was independent of ionic strength. Results of an X-ray photoelectron spectroscopy (XPS) analysis showed that Eu(III) was chemically present within the near-surface of TiO2 due to the formation of triple bond SOEu and triple bond SOHAEu complexes. An extended X-ray absorption fine structure (EXAFS) technique was applied to characterize the local structural environment of the adsorbed Eu(III), and the results indicated that Eu(III) was bound to about seven or eight O atoms at a distance of about 2.40 A. The functional groups of surface-bound HA were expected to be involved in the sorption process. The measured Eu-Ti distance confirmed the formation of inner-sphere sorption complexes on a TiO2 surface.

Thiophenic compounds adsorption on Na(I)Y and rare earth exchanged Y zeolites: a density functional theory study.

PubMed

Gao, Xionghou; Geng, Wei; Zhang, Haitao; Zhao, Xuefei; Yao, Xiaojun

2013-11-01

We have theoretically investigated the adsorption of thiophene, benzothiophene, dibenzothiophene on Na(I)Y and rare earth exchanged La(III)Y, Ce(III)Y, Pr(III)Y Nd(III)Y zeolites by density functional theory calculations. The calculated results show that except benzothiophene adsorbed on Na(I)Y with a stand configuration, the stable adsorption structures of other thiophenic compounds on zeolites exhibit lying configurations. Adsorption energies of thiophenic compounds on the Na(I)Y are very low, and decrease with the increase of the number of benzene rings in thiophenic compounds. All rare earth exchanged zeolites exhibit strong interaction with thiophene. La(III)Y and Nd(III)Y zeolites are found to show enhanced adsorption energies to benzothiophene and Pr(III)Y zeolites are favorable for dibenzothiophene adsorption. The analysis of the electronic total charge density and electron orbital overlaps show that the thiophenic compounds interact with zeolites by π-electrons of thiophene ring and exchanged metal atom. Mulliken charge populations analysis reveals that adsorption energies are strongly dependent on the charge transfer of thiophenic molecule and exchanged metal atom.

Assembly and Succession of Iron Oxide Microbial Mat Communities in Acidic Geothermal Springs

DOE PAGES

Beam, Jacob P.; Bernstein, Hans C.; Jay, Zackary J.; ...

2016-02-15

Biomineralized ferric oxide microbial mats are ubiquitous features on Earth, are common in hot springs of Yellowstone National Park (YNP, WY, USA), and form due to direct interaction between microbial and physicochemical processes. The overall goal of this study was to determine the contribution of different community members to the assembly and succession of acidic high-temperature Fe(III)-oxide mat ecosystems. Spatial and temporal changes in Fe(III)-oxide accretion and the abundance of relevant community members were monitored over 70 days using sterile glass microscope slides incubated in the outflow channels of two acidic geothermal springs (pH = 3-3.5; temperature = 68-75°C) inmore » YNP. Hydrogenobaculum spp. were the most abundant taxon identified during early successional stages (4-40 days), and have been shown to oxidize arsenite, sulfide, and hydrogen coupled to oxygen reduction. Iron-oxidizing populations of Metallosphaera yellowstonensis were detected within 4 days, and reached steady-state levels within 14-30 days, corresponding to visible Fe(III)-oxide accretion. Heterotrophic archaea colonized near 30 days, and emerged as the dominant functional guild after 70 days and in mature Fe(III)-oxide mats (1-2 cm thick). First-order rate constants of Fe(III)-oxide accretion ranged from 0.046 to 0.05 day -1 , and in situ microelectrode measurements showed that the oxidation of Fe(II) is limited by the diffusion of O2 into the Fe(III)-oxide mat. The formation of microterracettes also implicated O2 as a major variable controlling microbial growth and subsequent mat morphology. The assembly and succession of Fe(III)-oxide mat communities follows a repeatable pattern of colonization by lithoautotrophic organisms, and the subsequent growth of diverse organoheterotrophs. The unique geochemical signatures and micromorphology of extant biomineralized Fe(III)-oxide mats are also useful for understanding other Fe(II)-oxidizing systems.« less

Assembly and Succession of Iron Oxide Microbial Mat Communities in Acidic Geothermal Springs

PubMed Central

Beam, Jacob P.; Bernstein, Hans C.; Jay, Zackary J.; Kozubal, Mark A.; Jennings, Ryan deM.; Tringe, Susannah G.; Inskeep, William P.

2016-01-01

Biomineralized ferric oxide microbial mats are ubiquitous features on Earth, are common in hot springs of Yellowstone National Park (YNP, WY, USA), and form due to direct interaction between microbial and physicochemical processes. The overall goal of this study was to determine the contribution of different community members to the assembly and succession of acidic high-temperature Fe(III)-oxide mat ecosystems. Spatial and temporal changes in Fe(III)-oxide accretion and the abundance of relevant community members were monitored over 70 days using sterile glass microscope slides incubated in the outflow channels of two acidic geothermal springs (pH = 3–3.5; temperature = 68–75°C) in YNP. Hydrogenobaculum spp. were the most abundant taxon identified during early successional stages (4–40 days), and have been shown to oxidize arsenite, sulfide, and hydrogen coupled to oxygen reduction. Iron-oxidizing populations of Metallosphaera yellowstonensis were detected within 4 days, and reached steady-state levels within 14–30 days, corresponding to visible Fe(III)-oxide accretion. Heterotrophic archaea colonized near 30 days, and emerged as the dominant functional guild after 70 days and in mature Fe(III)-oxide mats (1–2 cm thick). First-order rate constants of Fe(III)-oxide accretion ranged from 0.046 to 0.05 day−1, and in situ microelectrode measurements showed that the oxidation of Fe(II) is limited by the diffusion of O2 into the Fe(III)-oxide mat. The formation of microterracettes also implicated O2 as a major variable controlling microbial growth and subsequent mat morphology. The assembly and succession of Fe(III)-oxide mat communities follows a repeatable pattern of colonization by lithoautotrophic organisms, and the subsequent growth of diverse organoheterotrophs. The unique geochemical signatures and micromorphology of extant biomineralized Fe(III)-oxide mats are also useful for understanding other Fe(II)-oxidizing systems. PMID:26913020

Assembly and Succession of Iron Oxide Microbial Mat Communities in Acidic Geothermal Springs.

PubMed

Beam, Jacob P; Bernstein, Hans C; Jay, Zackary J; Kozubal, Mark A; Jennings, Ryan deM; Tringe, Susannah G; Inskeep, William P

2016-01-01

Biomineralized ferric oxide microbial mats are ubiquitous features on Earth, are common in hot springs of Yellowstone National Park (YNP, WY, USA), and form due to direct interaction between microbial and physicochemical processes. The overall goal of this study was to determine the contribution of different community members to the assembly and succession of acidic high-temperature Fe(III)-oxide mat ecosystems. Spatial and temporal changes in Fe(III)-oxide accretion and the abundance of relevant community members were monitored over 70 days using sterile glass microscope slides incubated in the outflow channels of two acidic geothermal springs (pH = 3-3.5; temperature = 68-75°C) in YNP. Hydrogenobaculum spp. were the most abundant taxon identified during early successional stages (4-40 days), and have been shown to oxidize arsenite, sulfide, and hydrogen coupled to oxygen reduction. Iron-oxidizing populations of Metallosphaera yellowstonensis were detected within 4 days, and reached steady-state levels within 14-30 days, corresponding to visible Fe(III)-oxide accretion. Heterotrophic archaea colonized near 30 days, and emerged as the dominant functional guild after 70 days and in mature Fe(III)-oxide mats (1-2 cm thick). First-order rate constants of Fe(III)-oxide accretion ranged from 0.046 to 0.05 day(-1), and in situ microelectrode measurements showed that the oxidation of Fe(II) is limited by the diffusion of O2 into the Fe(III)-oxide mat. The formation of microterracettes also implicated O2 as a major variable controlling microbial growth and subsequent mat morphology. The assembly and succession of Fe(III)-oxide mat communities follows a repeatable pattern of colonization by lithoautotrophic organisms, and the subsequent growth of diverse organoheterotrophs. The unique geochemical signatures and micromorphology of extant biomineralized Fe(III)-oxide mats are also useful for understanding other Fe(II)-oxidizing systems.

Apolipoprotein C-III in triglyceride-rich lipoprotein metabolism.

PubMed

Ramms, Bastian; Gordts, Philip L S M

2018-06-01

Apolipoprotein (apo) C-III is a key player in triglyceride-rich lipoprotein metabolism and strongly associated with elevated plasma triglyceride levels. Several new studies added important insights on apoC-III and its physiological function confirming its promise as a valid therapeutic target. APOC3 is expressed in liver and intestine and regulates triglyceride-rich lipoprotein (TRL) catabolism and anabolism. The transcriptional regulation in both organs requires different regulatory elements. Clinical and preclinical studies established that apoC-III raises plasma triglyceride levels predominantly by inhibiting hepatic TRL clearance. Mechanistic insights into missense variants indicate accelerated renal clearance of apoC-III variants resulting in enhanced TRL catabolism. In contrast, an APOC3 gain-of-function variant enhances de novo lipogenesis and hepatic TRL production. Multiple studies confirmed the correlation between increased apoC-III levels and cardiovascular disease. This has opened up new therapeutic avenues allowing targeting of specific apoC-III properties in triglyceride metabolism. Novel in vivo models and APOC3 missense variants revealed unique mechanisms by which apoC-III inhibits TRL catabolism. Clinical trials with Volanesorsen, an APOC3 antisense oligonucleotide, report very promising lipid-lowering outcomes. However, future studies will need to address if acute apoC-III lowering will have the same clinical benefits as a life-long reduction.

Speciation of hexavalent chromium in welding fumes interference by air oxidation of chromium.

PubMed

Zatka, V J

1985-06-01

The determination of various chromium species in welding fume normally involves digestion in a hot alkaline solution. This work confirms that Cr(III) can be oxidized to Cr(VI) during this digestion. However, only dissolved forms of Cr(III), such as the hydroxochromate(III) ion, [Cr(OH)4], are susceptible to oxidation under these conditions. The air oxidation of Cr(III) can be prevented by hydrolytic destabilization of the hydroxochromate(III) complex by the presence of magnesium hydroxide precipitate. The procedure has been used successfully in the determination of insoluble chromium(VI) in welding fumes. Excellent reproducibility is documented for soluble and insoluble chromium(VI) fractions in the analysis of a bulk sample of welding fume.

Impaired renal function is associated with worse self-reported outcomes after kidney transplantation.

PubMed

Neri, Luca; Dukes, Jonathan; Brennan, Daniel C; Salvalaggio, Paulo R; Seelam, Susmitha; Desiraju, Srividya; Schnitzler, Mark

2011-12-01

We sought to determine the association between health-related quality of life (HRQOL) and graft function in renal transplant recipients. We enrolled 577 kidney transplant recipients aged 18-74 years (response rate 87%). Recipients with multiple or multi-organ transplantation, creatine kinase >200 U/L, acute renal failure or cellular rejection (n = 64), and without creatinine assessments in 3 months pre-enrollment (n = 127) were excluded. The questionnaire included Euro QOL 5 Dimensions (EQ-5D), Health Utility Index III (HUI-III), Kidney Disease Quality of Life-36 (KDQOL36) which include a generic section (RAND SF-12). Data on medical conditions, therapy regimens, and biochemistry results were extracted from clinical charts. We used general linear models adjusted for demographic, socioeconomic, and clinical characteristics to assess the association between HRQOL and severity of chronic kidney disease (CKD). Patients with more advanced CKD were more likely to be African-American, covered by public insurance, more likely to have shorter time after transplantation, higher phosphorus and lower hemoglobin, serum albumin, and calcium levels. All HRQOL scales were inversely associated with CKD severity. All associations were robust to adjustment for possible confounders. Several health-related quality of life dimensions may be affected by poor renal function after transplantation.

Effect of Grade I and II Intraventricular Hemorrhage on Visuocortical Function in Very Low Birth Weight Infants

PubMed Central

Madan, Ashima; Norcia, Anthony M.; Hou, Chuan; Pettet, Mark W.; Good, William V.

2015-01-01

The neurological outcome for infants with Grade I/II intraventricular hemorrhage (IVH) is debated. The aim of this study was to determine whether very low birth weight infants (VLBW, < 1500 g) with Grade I /II (IVH) have altered visuocortical activity compared with infants with no IVH. We assessed the quantitative swept parameter Visual Evoked Potential (sVEP) responses evoked by three different visual stimuli. Data from 52 VLBW infants were compared with data from 13 infants with Grade I or II IVH, enrolled at 5 – 7 months corrected age. Acuity thresholds and suprathreshold response amplitudes were compared. Grating Acuity (GA), Contrast Sensitivity (CS) and Vernier Acuity (VA) were each worse in the Grade I/ II IVH compared with the no IVH groups (8.24 cpd in IVH group vs 13.07 cpd in no IVH group for GA; 1.44% vs 1.18% for CS and 1.55 arcmin vs 0.58 arcmin for VA). The slopes of the response amplitude for CS and VA were significantly lower in IVH infants. The spatial frequency tuning function was shifted downward on the spatial frequency axis, without a change in slope. These results indicate that Grade I/II IVH are associated with deleterious effects on cortical vision development and function. PMID:22371027

Voltammetric determination of arsenic in high iron and manganese groundwaters.

PubMed

Gibbon-Walsh, Kristoff; Salaün, Pascal; Uroic, M Kalle; Feldmann, Joerg; McArthur, John M; van den Berg, Constant M G

2011-09-15

Determination of the speciation of arsenic in groundwaters, using cathodic stripping voltammetry (CSV), is severely hampered by high levels of iron and manganese. Experiments showed that the interference is eliminated by addition of EDTA, making it possible to determine the arsenic speciation on-site by CSV. This work presents the CSV method to determine As(III) in high-iron or -manganese groundwaters in the field with only minor sample treatment. The method was field-tested in West-Bengal (India) on a series of groundwater samples. Total arsenic was subsequently determined after acidification to pH 1 by anodic stripping voltammetry (ASV). Comparative measurements by ICP-MS as reference method for total As, and by HPLC for its speciation, were used to corroborate the field data in stored samples. Most of the arsenic (78±0.02%) was found to occur as inorganic As(III) in the freshly collected waters, in accordance with previous studies. The data shows that the modified on-site CSV method for As(III) is a good measure of water contamination with As. The EDTA was also found to be effective in stabilising the arsenic speciation for longterm sample storage at room temperature. Without sample preservation, in water exposed to air and sunlight, the As(III) was found to become oxidised to As(V), and Fe(II) oxidised to Fe(III), removing the As(V) by adsorption on precipitating Fe(III)-hydroxides within a few hours. Copyright © 2011 Elsevier B.V. All rights reserved.

Effects of rare earth and acid rain pollution on plant chloroplast ATP synthase and element contents at different growth stages.

PubMed

Zhang, Fan; Hu, Huiqing; Wang, Lihong; Zhou, Qing; Huang, Xiaohua

2018-03-01

Combined rare earth and acid rain pollution has become a new environmental problem, seriously affecting plant survival. The effects of these two kinds of pollutants on plant photosynthesis have been reported, but the micro mechanisms are not very clear. In this research, we studied the effects of lanthanum [La(III), 0.08, 1.20 and 2.40 mM] and acid rain (pH value = 2.5, 3.5 and 4.5) on the ATPase activity and gene transcription level and the functional element contents in rice leaf chloroplasts. The results showed that the combined 0.08 mM La(III) and pH 4.5 acid rain increased the ATPase activity and gene transcription level as well as contents of some functional elements. But other combined treatments of acid rain and La(III) reduced the ATPase activity and gene transcription level as well as functional element contents. The change magnitude of the above indexes at rice booting stage was greater than that in seedling stage or grain filling stage. These results reveal that effects of La(III) and acid rain on ATPase activity and functional element contents in rice leaf chloroplasts are related to the combination of La(III) dose and acid rain intensity and the plant growth stage. In addition, the changes in the ATPase activity were related to ATPase gene transcription level. This study would provide a reference for understanding the microcosmic mechanism of rare earth and acid rain pollution on plant photosynthesis and contribute to evaluate the possible environmental risks associated with combined La(III) and acid rain pollution. The effects of La(III) and acid rain on activity and gene transcription level of rice chloroplast ATPase and contents of functional elements were different at different growth stages. Copyright © 2017 Elsevier Ltd. All rights reserved.

Subunit compositions of Arabidopsis RNA polymerases I and III reveal Pol I- and Pol III-specific forms of the AC40 subunit and alternative forms of the C53 subunit

DOE PAGES

Ream, Thomas S.; Haag, Jeremy R.; Pontvianne, Frederic; ...

2015-05-02

Using affinity purification and mass spectrometry, we identified the subunits of Arabidopsis thaliana multisubunit RNA Polymerases I and III (abbreviated as Pol I and Pol III), providing the first description of their physical compositions in plants. AC40 and AC19 subunits are typically common to Pol I (a.k.a. Pol A) and Pol III (a.k.a. Pol C) and are encoded by single genes whose mutation, in humans, is a cause of the craniofacial disorder, Treacher-Collins Syndrome. Surprisingly, A. thaliana, and related species, express two distinct AC40 paralogs, one of which assembles into Pol I and the other of which assembles into Polmore » III. Changes at eight amino acid positions correlate with this functional divergence of Pol I and Pol III-specific AC40 paralogs. Two genes encode homologs of the yeast C53 subunit, and either variant can assemble into Pol III. By contrast, only one of two potential C17 variants, and one of two potential C31 variants were detected in Pol III. We introduce a new nomenclature system for plant Pol I and Pol III subunits in which the twelve subunits that are structurally and functionally homologous among Pols I through V are assigned equivalent numbers.« less

Subunit compositions of Arabidopsis RNA polymerases I and III reveal Pol I- and Pol III-specific forms of the AC40 subunit and alternative forms of the C53 subunit

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ream, Thomas S.; Haag, Jeremy R.; Pontvianne, Frederic

Using affinity purification and mass spectrometry, we identified the subunits of Arabidopsis thaliana multisubunit RNA Polymerases I and III (abbreviated as Pol I and Pol III), providing the first description of their physical compositions in plants. AC40 and AC19 subunits are typically common to Pol I (a.k.a. Pol A) and Pol III (a.k.a. Pol C) and are encoded by single genes whose mutation, in humans, is a cause of the craniofacial disorder, Treacher-Collins Syndrome. Surprisingly, A. thaliana, and related species, express two distinct AC40 paralogs, one of which assembles into Pol I and the other of which assembles into Polmore » III. Changes at eight amino acid positions correlate with this functional divergence of Pol I and Pol III-specific AC40 paralogs. Two genes encode homologs of the yeast C53 subunit, and either variant can assemble into Pol III. By contrast, only one of two potential C17 variants, and one of two potential C31 variants were detected in Pol III. We introduce a new nomenclature system for plant Pol I and Pol III subunits in which the twelve subunits that are structurally and functionally homologous among Pols I through V are assigned equivalent numbers.« less

Ultrasonic irradiation enhanced the ability of Fluorescein-DA-Fe(III) on sonodynamic and sonocatalytic damages of DNA molecules.

PubMed

Wu, Qiong; Chen, Xia; Jia, Lizhen; Wang, Yi; Sun, Ying; Huang, Xingjun; Shen, Yuxiang; Wang, Jun

2017-11-01

The interaction of DNA with Bis [N,N-bis (carboxymethyl) aminomethyl] fluorescein-Ferrous(III) (Fluorescein-DA-Fe(III)) with dual functional (sonodynamic and sonocatalytic) activity was studied by UV-vis spectroscopy, fluorescence spectroscopy, FT-IR spectroscopy, circular dichroism (CD) spectroscopy and viscosity measurements. And then, the damage of DNA caused by Fluorescein-DA-Fe(III) under ultrasonic irradiation (US) was researched by agarose gel electrophoresis and cytotoxicity assay. Meanwhile, some influenced factors such as ultrasonic irradiation time and Fluorescein-DA-Fe(III) concentration on the damage degree of DNA molecules were also examined. As a control, for Bis [N,N-bis (carboxymethyl) aminomethyl] fluorescein (Fluorescein-DA), the same experiments were carried out. The results showed that both Fluorescein-DA-Fe(III) and Fluorescein-DA can interact with DNA molecules. Under ultrasonic irradiation, Fluorescein-DA shows sonodynamic activity, which can damage DNA molecules. While, in the presence of Fe(III) ion, the Fluorescein-DA-Fe(III) displays not only sonodynamic activity but also sonocatalytic activity under ultrasonic irradiation, which injures DNA more serious than Fluorescein-DA. The researches confirmed the dual function (sonodynamic activity and sonocatalytic activity) of Fluorescein-DA-Fe(III) and expanded the usage of Fluorescein-DA-Fe(III) as a sonosensitizer in sonodynamic therapy (SDT). Copyright © 2017 Elsevier B.V. All rights reserved.

[Orthodontic treatment of Class III patients with mandibular asymmetry].

PubMed

Duan, Yin-Zhong; Huo, Na; Chen, Lei; Chen, Xue-Peng; Lin, Yang

2008-12-01

To investigate the treatment outcome of Class III patients with dental, functional and mild skeletal mandibular asymmetry. Thirty-five patients (14 males and 21 females) with dental, functional and mild skeletal mandibular asymmetry were selected. The age range of the patients was 7 - 22 years with a mean age of 16.5 years. Dental mandibular asymmetry was treated with expansion of maxillary arch to help the mandible returning to normal position. Functional mandibular asymmetry was treated with activator or asymmetrical protraction and Class III elastics. Mild skeletal mandibular asymmetry was treated with camouflage treatment. Good occlusal relationships were achieved and facial esthetics was greatly improved after orthodontic treatment in patients with dental and functional mandibular asymmetry. However, patients with skeletal mandibular asymmetry should be treated with both extraction and genioplasty. Orthodontic treatment was suitable for patients with dental and functional mandibular asymmetry, while combined orthodontics and surgery could get good results in patients with skeletal mandibular asymmetry.

Solid phase extraction of gold(III) on attapulgite modified with triocarbohydrazide prior to its determination in environmental samples by ICP-OES.

PubMed

Zhang, Li; Li, Zhenhua; Hu, Zheng; Chang, Xijun

2011-09-01

The first study on the high efficiency of triocarbohydrazide modified attapulgite as solid-phase extractant for preconcentration of trace Au(III) prior to the measurement by inductively coupled plasma optical emission spectrometry (ICP-OES) has been reported. Experimental conditions for effective adsorption of trace levels of Au(III) were optimized with respect to different experimental parameters using batch and column procedures in detail. At pH 3, Au(III) could be quantitatively adsorbed on the new sorbent, and the adsorbed Au(III) could be completely eluted from the sorbent surface by 2.0mL 1.0molL(-1) of HCl+2% CS(NH(2))(2) solution. An enrichment factor of 150 was accomplished. Moreover, common interfering ions did not interfere in both separation and determination. The maximum adsorption capacity of the sorbent for Au(III) was found to be 66.7mgg(-1). The detection limit (3σ) of this method was 0.32μgL(-1) and the relative standard deviation (RSD) was 3.3% (n=8). The method, with high selectivity, sensitivity and reproducibility, was validated using certified reference materials, and had been applied for the determination of trace Au(III) with satisfactory results. Copyright © 2011 Elsevier B.V. All rights reserved.

Evaluating the role of functional impairment in personality psychopathology.

PubMed

Boland, Jennifer K; Damnjanovic, Tatjana; Anderson, Jaime L

2018-03-22

DSM-5's Section III Alternative Model for Personality Disorder (AMPD) model states that an individual must show impairment in self and interpersonal functioning for PD diagnosis. The current study investigated dimensional personality trait associations with impairment, including differential patterns of impairment across specific PDs, and whether traits have improved our assessment of functional impairment in PDs. Two-hundred and seventy-seven participants were administered measures of Antisocial PD, Avoidant PD, Borderline PD, Narcissistic PD, Obsessive-Compulsive PD, and Schizotypal PD from the perspectives of Section II (PDQ-4) and Section III (PID-5) PD models, as well as measures of functional impairment in interpersonal and intrapersonal domains. Pearson correlations showed associations between ratings of impairment and most Section II and Section III PDs and trait facets, with the exception of narcissistic PD. Hierarchical regression analyses revealed that Section III PDs added predictive validity beyond Section II PDs in predicting impairment, except narcissistic PD. These findings provide support both for the impairment criterion in the AMPD and for the association between trait-based PDs and impairment, and suggest that this trait-based measurement adds uniquely to the understanding of functional impairment. Copyright © 2018. Published by Elsevier B.V.

A paradox of transcriptional and functional innate interferon responses of human intestinal enteroids to enteric virus infection.

PubMed

Saxena, Kapil; Simon, Lukas M; Zeng, Xi-Lei; Blutt, Sarah E; Crawford, Sue E; Sastri, Narayan P; Karandikar, Umesh C; Ajami, Nadim J; Zachos, Nicholas C; Kovbasnjuk, Olga; Donowitz, Mark; Conner, Margaret E; Shaw, Chad A; Estes, Mary K

2017-01-24

The intestinal epithelium can limit enteric pathogens by producing antiviral cytokines, such as IFNs. Type I IFN (IFN-α/β) and type III IFN (IFN-λ) function at the epithelial level, and their respective efficacies depend on the specific pathogen and site of infection. However, the roles of type I and type III IFN in restricting human enteric viruses are poorly characterized as a result of the difficulties in cultivating these viruses in vitro and directly obtaining control and infected small intestinal human tissue. We infected nontransformed human intestinal enteroid cultures from multiple individuals with human rotavirus (HRV) and assessed the host epithelial response by using RNA-sequencing and functional assays. The dominant transcriptional pathway induced by HRV infection is a type III IFN-regulated response. Early after HRV infection, low levels of type III IFN protein activate IFN-stimulated genes. However, this endogenous response does not restrict HRV replication because replication-competent HRV antagonizes the type III IFN response at pre- and posttranscriptional levels. In contrast, exogenous IFN treatment restricts HRV replication, with type I IFN being more potent than type III IFN, suggesting that extraepithelial sources of type I IFN may be the critical IFN for limiting enteric virus replication in the human intestine.

A paradox of transcriptional and functional innate interferon responses of human intestinal enteroids to enteric virus infection

PubMed Central

Saxena, Kapil; Simon, Lukas M.; Zeng, Xi-Lei; Blutt, Sarah E.; Crawford, Sue E.; Sastri, Narayan P.; Karandikar, Umesh C.; Ajami, Nadim J.; Zachos, Nicholas C.; Kovbasnjuk, Olga; Donowitz, Mark; Conner, Margaret E.; Shaw, Chad A.; Estes, Mary K.

2017-01-01

The intestinal epithelium can limit enteric pathogens by producing antiviral cytokines, such as IFNs. Type I IFN (IFN-α/β) and type III IFN (IFN-λ) function at the epithelial level, and their respective efficacies depend on the specific pathogen and site of infection. However, the roles of type I and type III IFN in restricting human enteric viruses are poorly characterized as a result of the difficulties in cultivating these viruses in vitro and directly obtaining control and infected small intestinal human tissue. We infected nontransformed human intestinal enteroid cultures from multiple individuals with human rotavirus (HRV) and assessed the host epithelial response by using RNA-sequencing and functional assays. The dominant transcriptional pathway induced by HRV infection is a type III IFN-regulated response. Early after HRV infection, low levels of type III IFN protein activate IFN-stimulated genes. However, this endogenous response does not restrict HRV replication because replication-competent HRV antagonizes the type III IFN response at pre- and posttranscriptional levels. In contrast, exogenous IFN treatment restricts HRV replication, with type I IFN being more potent than type III IFN, suggesting that extraepithelial sources of type I IFN may be the critical IFN for limiting enteric virus replication in the human intestine. PMID:28069942

III-Nitride, SiC and Diamond Materials for Electronic Devices. Symposium Held April 8-12 1996, San Francisco, California, U.S.A. Volume 423.

DTIC Science & Technology

1996-12-01

gallium, nitrogen and gallium nitride structures. Thus it can be shown to be transferable and efficient for predictive molecular -dynamic simulations on...potentials and forces for the molecular dynamics simulations are derived by means of a density-functional based nonorthogonal tight-binding (DF-TB) scheme...LDA). Molecular -dynamics simulations for determining the different reconstructions of the SiC surface use the slab method (two-dimensional periodic

Transvertebral direct current stimulation paired with locomotor training in chronic spinal cord injury: A case study.

PubMed

Powell, Elizabeth Salmon; Carrico, Cheryl; Raithatha, Ravi; Salyers, Emily; Ward, Andrea; Sawaki, Lumy

2016-01-01

This double-blind, sham-controlled, crossover case study combined transvertebral direct current stimulation (tvDCS) and locomotor training on a robot-assisted gait orthosis (LT-RGO). Determine whether cathodal tvDCS paired with LT-RGO leads to greater changes in function and neuroplasticity than sham tvDCS paired with LT-RGO. University of Kentucky (UK) HealthCare Stroke and Spinal Cord Neurorehabilitation Research at HealthSouth Cardinal Hill Hospital. A single subject with motor incomplete spinal cord injury (SCI) participated in 24 sessions of sham tvDCS paired with LT-RGO before crossover to 24 sessions of cathodal tvDCS paired with LT-RGO. Functional outcomes were measured with 10 Meter Walk Test (10MWT), 6 Minute Walk Test (6MWT), Spinal Cord Independence Measure-III (SCIM-III) mobility component, lower extremity manual muscle test (MMT), and Berg Balance Scale (BBS). Corticospinal changes were assessed using transcranial magnetic stimulation. Improvement in 10MWT speed, SCIM-III mobility component, and BBS occurred with both conditions. 6MWT worsened after sham tvDCS and improved after cathodal tvDCS. MMT scores for both lower extremities improved following sham tvDCS but decreased following cathodal tvDCS. Corticospinal excitability increased following cathodal tvDCS but not sham tvDCS. These results suggest that combining cathodal tvDCS and LT-RGO may improve functional outcomes, increase corticospinal excitability, and possibly decrease spasticity. Randomized controlled trials are needed to confirm these conclusions. This publication was supported by the National Center for Research Resources and the National Center for Advancing Translational Sciences, National Institutes of Health, through Grant UL1TR000117, and the HealthSouth Cardinal Hill Stroke and Spinal Cord Endowment (1215375670).

Interplay of HD-Zip II and III transcription factors in auxin-regulated plant development.

PubMed

Turchi, L; Baima, S; Morelli, G; Ruberti, I

2015-08-01

The homeodomain-leucine zipper (HD-Zip) class of transcription factors is unique to plants. HD-Zip proteins bind to DNA exclusively as dimers recognizing dyad symmetric sequences and act as positive or negative regulators of gene expression. On the basis of sequence homology in the HD-Zip DNA-binding domain, HD-Zip proteins have been grouped into four families (HD-Zip I-IV). Each HD-Zip family can be further divided into subfamilies containing paralogous genes that have arisen through genome duplication. Remarkably, all the members of the HD-Zip IIγ and -δ clades are regulated by light quality changes that induce in the majority of the angiosperms the shade-avoidance response, a process regulated at multiple levels by auxin. Intriguingly, it has recently emerged that, apart from their function in shade avoidance, the HD-Zip IIγ and -δ transcription factors control several auxin-regulated developmental processes, including apical embryo patterning, lateral organ polarity, and gynoecium development, in a white-light environment. This review presents recent advances in our understanding of HD-Zip II protein function in plant development, with particular emphasis on the impact of loss-of-function HD-Zip II mutations on auxin distribution and response. The review also describes evidence demonstrating that HD-Zip IIγ and -δ genes are directly and positively regulated by HD-Zip III transcription factors, primary determinants of apical shoot development, known to control the expression of several auxin biosynthesis, transport, and response genes. Finally, the interplay between HD-Zip II and III transcription factors in embryo apical patterning and organ polarity is discussed. © The Author 2015. Published by Oxford University Press on behalf of the Society for Experimental Biology. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Malfunctioning of the iron-sulfur cluster assembly machinery in Saccharomyces cerevisiae produces oxidative stress via an iron-dependent mechanism, causing dysfunction in respiratory complexes.

PubMed

Gomez, Mauricio; Pérez-Gallardo, Rocío V; Sánchez, Luis A; Díaz-Pérez, Alma L; Cortés-Rojo, Christian; Meza Carmen, Victor; Saavedra-Molina, Alfredo; Lara-Romero, Javier; Jiménez-Sandoval, Sergio; Rodríguez, Francisco; Rodríguez-Zavala, José S; Campos-García, Jesús

2014-01-01

Biogenesis and recycling of iron-sulfur (Fe-S) clusters play important roles in the iron homeostasis mechanisms involved in mitochondrial function. In Saccharomyces cerevisiae, the Fe-S clusters are assembled into apoproteins by the iron-sulfur cluster machinery (ISC). The aim of the present study was to determine the effects of ISC gene deletion and consequent iron release under oxidative stress conditions on mitochondrial functionality in S. cerevisiae. Reactive oxygen species (ROS) generation, caused by H2O2, menadione, or ethanol, was associated with a loss of iron homeostasis and exacerbated by ISC system dysfunction. ISC mutants showed increased free Fe2+ content, exacerbated by ROS-inducers, causing an increase in ROS, which was decreased by the addition of an iron chelator. Our study suggests that the increment in free Fe2+ associated with ROS generation may have originated from mitochondria, probably Fe-S cluster proteins, under both normal and oxidative stress conditions, suggesting that Fe-S cluster anabolism is affected. Raman spectroscopy analysis and immunoblotting indicated that in mitochondria from SSQ1 and ISA1 mutants, the content of [Fe-S] centers was decreased, as was formation of Rieske protein-dependent supercomplex III2IV2, but this was not observed in the iron-deficient ATX1 and MRS4 mutants. In addition, the activity of complexes II and IV from the electron transport chain (ETC) was impaired or totally abolished in SSQ1 and ISA1 mutants. These results confirm that the ISC system plays important roles in iron homeostasis, ROS stress, and in assembly of supercomplexes III2IV2 and III2IV1, thus affecting the functionality of the respiratory chain.

Investigation of complexes tannic acid and myricetin with Fe(III)

NASA Astrophysics Data System (ADS)

Sungur, Şana; Uzar, Atike

2008-01-01

The pH dependence of the complexes was determined by both potentiometric and spectrophotometric studies. Stability constants and stoichiometries of the formed complexes were determined using slope ratio method. Fe(III) was formed complexes with tannic acid of various stoichiometries, which in the 1:1 molar ratio at pH < 3, in the 2:1 molar ratio at pH 3-7 and in the 4:1 molar ratio at pH > 7. Fe(III) was formed complexes with myricetin in the 1:2 molar ratio at pH 4 and 5 and in the 1:1 molar ratio at pH 6. Stability constant values were found to be 10 5 to 10 17 and 10 5 to 10 9 for Fe(III)-tannic acid complexes and Fe(III)-myricetin complexes. Both tannic acid and myricetin were possessed minimum affinities to Cu(II) and Zn(II). They had less affinity for Al(III) than for Fe(III).

The efficacy of GMFM-88 and GMFM-66 to detect changes in gross motor function in children with cerebral palsy (CP): a literature review.

PubMed

Alotaibi, Madawi; Long, Toby; Kennedy, Elizabeth; Bavishi, Siddhi

2014-01-01

The purpose of this study was to review published research on the use of the Gross Motor Function Measure (GMFM-88) and (GMFM-66) as outcome measures to determine if these tools detect changes in gross motor function in children with cerebral palsy (CP) undergoing interventions. A comprehensive literature search was conducted using Medline and PubMed to identify studies published from January 2000 through January 2011 that reported the accuracy of GMFM-88 and GMFM-66 to measure changes over time in children with CP undergoing interventions. The keywords used for the search were "GMFM" and "CP". Two of the authors (M.A. and S.B.) reviewed the titles and abstracts found in the databases. The methodological quality of the studies was assessed by using the Critical Review Form-Quantitative Studies. Of 62 papers initially identified, 21 studies fulfilled the inclusion criteria. These articles consist of three longitudinal studies, six randomized controlled trials, four repeated measure design, six pre-post test design, a case series and one non-randomized prospective study. The included studies were generally of moderate to high methodological quality. The studies included children from a wide age range of 10 months to 16 years. According to the National Health and Medical Research Council, the study designs were level II, III-2, III-3 and IV. The review suggests that the GMFM-88 and GMFM-66 are useful as outcome measures to detect changes in gross motor function in children with CP undergoing interventions. Implications for Rehabilitation Accurate measurement of change in gross motor skill acquisition is important to determine effectiveness of intervention programs in children with cerebral palsy (CP). The Gross Motor Function Measure (GMFM-88 and GMFM-66) are common tools used by rehabilitation specialists to measure gross motor function in children with CP. The GMFM appears to be an effective outcome tool for measuring change in gross motor function according to a small number of randomized control studies utilizing participant populations of convenience.

Chemiluminescence of the reaction system Ce(IV)-non-steroidal anti-inflammatory drugs containing europium(III) ions and its application to the determination of naproxen in pharmaceutical preparations and urine.

PubMed

Kaczmarek, Małgorzata

2011-11-01

The chemiluminescence (CL) of oxidation of non-steroidal anti-inflammatory drugs (NSAIDs) by Ce(IV) ions, was recorded in the presence and absence europium(III) ions, in solution of pH ~ 4 of solution. Kinetic curves and CL emission spectra of the all studied systems were discussed. CL of measurable intensity was observed in the Ce(IV)-NP-Eu(III) reaction system only in acidic solutions. The CL spectrum rcegistered for this system shows emission bands, typical of Eu(III) ions, with maximum at λ ~ 600 nm. The chemiluminescent method, based on Eu(III) emission in reaction system of NP-Ce(IV)-Eu(III) in acid solution was therefore used for the determination of naproxen in mixture of non-steroidal anti-inflammatory drugs.

Latent transforming growth factor beta1 activation in situ: quantitative and functional evidence after low-dose gamma-irradiation

NASA Technical Reports Server (NTRS)

Ehrhart, E. J.; Segarini, P.; Tsang, M. L.; Carroll, A. G.; Barcellos-Hoff, M. H.; Chatterjee, A. (Principal Investigator)

1997-01-01

The biological activity of transforming growth factor beta1 (TGF-beta) is controlled by its secretion as a latent complex in which it is noncovalently associated with latency-associated peptide (LAP). Activation is the extracellular process in which TGF-beta is released from LAP, and is considered to be a primary regulatory control. We recently reported rapid and persistent changes in TGF-beta immunoreactivity in conjunction with extracellular matrix remodeling in gamma-irradiated mouse mammary gland. Our hypothesis is that these specific changes in immunoreactivity are indicative of latent TGF-beta activation. In the present study, we determined the radiation dose response and tested whether a functional relationship exists between radiation-induced TGF-beta and collagen type III remodeling. After radiation exposures as low as 0.1 Gy, we detected increased TGF-beta immunoreactivity in the mammary epithelium concomitant with decreased LAP immunostaining, which are events consistent with activation. Quantitative image analysis demonstrated a significant (P=0.0005) response at 0.1 Gy without an apparent threshold and a linear dose response to 5 Gy. However, in the adipose stroma, loss of LAP demonstrated a qualitative threshold at 0.5 Gy. Loss of LAP paralleled induction of collagen III immunoreactivity in this tissue compartment. We tested whether TGF-beta mediates collagen III expression by treating animals with TGF-beta panspecific monoclonal antibody, 1D11.16, administered i.p. shortly before irradiation. Radiation-induced collagen III staining in the adipose stroma was blocked in an antibody dose-dependent manner, which persisted through 7 days postirradiation. RNase protection assay revealed that radiation-induced elevation of total gland collagen III mRNA was also blocked by neutralizing antibody treatment. These data provide functional confirmation of the hypothesis that radiation exposure leads to latent TGF-beta activation, support our interpretation of the reciprocal shift in immunoreactivity as evidence of activation, and implicate TGF-beta as a mediator of tissue response to ionizing radiation. The sensitivity of activation to low radiation doses points to a potential role for TGF-beta in orchestrating tissue response to oxidative stress. As such, radiation may be useful as a probe to delineate the consequences of latent TGF-beta activation in situ.

Large Hexadecametallic {Mn(III) -Ln(III) } Wheels: Synthesis, Structural, Magnetic, and Theoretical Characterization.

PubMed

Vignesh, Kuduva R; Langley, Stuart K; Moubaraki, Boujemaa; Murray, Keith S; Rajaraman, Gopalan

2015-11-09

The synthesis, gas sorption studies, magnetic properties, and theoretical studies of new molecular wheels of core type {Mn(III) 8 Ln(III) 8 } (Ln=Dy, Ho, Er, Y and Yb), using the ligand mdeaH2 , in the presence of ortho-toluic or benzoic acid are reported. From the seven wheels studied the {Mn8 Dy8 } and {Mn8 Y8 } analogues exhibit SMM behavior as determined from ac susceptibility experiments in a zero static magnetic field. From DFT calculations a S=16 ground state was determined for the {Mn8 Y8 } complex due to weak ferromagnetic Mn(III) -Mn(III) interactions. Ab initio CASSCF+RASSI-SO calculations on the {Mn8 Dy8 } wheel estimated the Mn(III) -Dy(III) exchange interaction as -0.1 cm(-1) . This weak exchange along with unfavorable single-ion anisotropy of Dy(III) /Mn(III) ions, however, led to the observation of SMM behavior with fast magnetic relaxation. The orientation of the g-anisotropy of the Dy(III) ions is found to be perpendicular to the plane of the wheel and this suggests the possibility of toroidal magnetic moments in the cluster. The {Mn8 Ln8 } clusters reported here are the largest heterometallic Mn(III) Ln(III) wheels and the largest {3d-4f} wheels to exhibit SMM behavior reported to date. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Simultaneous determination of Cr(III) and Cr(VI) in tannery wastewater using low pressure ion chromatography combined with flow injection spectrophotometry

NASA Astrophysics Data System (ADS)

Chen, Shujuan; Zhang, Xinshen; Yu, Lingyun; Wang, Li; Li, Hui

2012-03-01

Trivalent and hexavalent chromium have been successfully separated and determined using low pressure ion chromatography combined with flow injection spectrophotometric analysis (LPIC-FIA). A column packed with crosslinking starch microspheres was used for on-line separation of Cr(III) from Cr(VI) in a flow-injection system because of its absorptive effect on Cr(III). To determine the concentration of Cr(III) and Cr(VI) in samples, we used 3.0 mmol/L nitric acid to elute adsorbed Cr(III) from the column and then used ceric sulfate-sulfuric acid as oxidant to convert all Cr(III) into Cr(VI). Then, Cr(VI) directly came from the samples and Cr(VI) came from Cr(III) successively formed a amaranthine complex with diphenycarbazide and the complex shows a maximum absorption at 530 nm. Analytical parameters including the concentration of eluent and oxidant solution, oxidizing temperature, length of oxidizing reaction coil, reaction coil and injection coil, interfering effects, etc., were optimized. The limit of detection was 1.25 μg/L for Cr(VI) and 3.76 μg/L for Cr(III). The linear relationship between absorption with the concentration of Cr(VI) and Cr(III) was 0.001-1.000 mg/L and 0.030-1.000 mg/L with correlation coefficients of 0.9995 and 0.9994, respectively. The relative standard deviation of Cr(VI) and Cr(III) was 1.21% and 1.66%, respectively (n = 10). Major cations and anions did not show any interference. We validated this method through certified reference materials and through measuring the recovery in tannery wastewater.

A Ni(iii) complex stabilized by silica nanoparticles as an efficient nanoheterogeneous catalyst for oxidative C-H fluoroalkylation.

PubMed

Khrizanforov, Mikhail N; Fedorenko, Svetlana V; Strekalova, Sofia O; Kholin, Kirill V; Mustafina, Asiya R; Zhilkin, Mikhail Ye; Khrizanforova, Vera V; Osin, Yuri N; Salnikov, Vadim V; Gryaznova, Tatyana V; Budnikova, Yulia H

2016-07-26

We have developed Ni(III)-doped silica nanoparticles ([(bpy)xNi(III)]@SiO2) as a recyclable, low-leaching, and efficient oxidative functionalization nanocatalyst for aromatic C-H bonds. The catalyst is obtained by doping the complex [(bpy)3Ni(II)] on silica nanoparticles along with its subsequent electrooxidation to [(bpy)xNi(III)] without an additional oxidant. The coupling reaction of arenes with perfluoroheptanoic acid occurs with 100% conversion of reactants in a single step at room temperature under nanoheterogeneous conditions. The catalyst content is only 1% with respect to the substrates under electrochemical regeneration conditions. The catalyst can be easily separated from the reaction mixture and reused a minimum of five times. The results emphasize immobilization on the silica support and the electrochemical regeneration of Ni(III) complexes as a facile route for developing an efficient nanocatalyst for oxidative functionalization.

Study of Silver Nanoparticles Sensitized Fluorescence and Second-Order Scattering of Terbium(III)-Pefloxacin Mesylate Complex and Determination of Pefloxacin Mesylate

PubMed Central

Li, Aiyun; Song, Zhiqiang

2014-01-01

α-Keto acid of pefloxacin mesylate (PFLX) can form the complex with Terbium(III). The intramolecular energy from PFLX to Terbium(III) ion takes place when excited, and thus Terbium(III) excited state is formed and then emits the characteristic fluorescence of Terbium(III), locating at 490, 545, 580, and 620 nm. The second-order scattering (SOS) peak at 545 nm also appears for the complex with the exciting wavelength of 273 nm. When the silver nanoparticles are added to the system, the luminescence intensity at 545 nm greatly increased. So, with the adding of nanoparticles to the Terbium(III)-PFLX complex, not only is the intramolecular energy promoted but also the SOS intensity is enhanced. The experimental results show that it is the silver nanoparticles with certain size and certain concentration which can greatly enhance the fluorescence-SOS intensity, and the relative intensity at 545 nm is proportional to the amount of PFLX. Based on this phenomenon, a novel method for the determination of PFLX has been developed and applied to the determination of PFLX in capsule and serum samples. PMID:24892083

Anion-exchange high-performance liquid chromatography of water-soluble chromium (VI) and chromium (III) complexes in biological materials.

PubMed

Suzuki, Y

1987-04-10

A high-performance anion-exchange liquid chromatograph coupled to visible-range (370 nm) and UV (280 nm) detectors and an atomic-absorption spectrometer allowed the rapid determination of CrVI and/or complexes of CrIII in rat plasma, erythrocyte lysate and liver supernatant treated with CrVI or CrIII in vitro. CrVI in the eluates was determined using both the visible-range detector and atomic-absorption spectrometer (AAS). The detection limits of CrVI in standard solutions using these methods were 2 and 5 ng (signal-to-noise ratio = 2), respectively. Separations of the biological components and of CrIII complexes were monitored by UV and AAS analyses, respectively. Time-related decreases of CrVI accompanied by increases in CrIII complexes were observed, indicating the reduction of CrVI by some of the biological components. The reduction rates were considerably higher in the liver supernatant and erythrocyte lysate than in the plasma. These results indicate that the anion-exchange high-performance liquid chromatographic system is useful for simultaneous determination of CrVI and CrIII complexes in biological materials.

Synthesis and Characterization of the Actinium Aquo Ion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferrier, Maryline G.; Stein, Benjamin W.; Batista, Enrique R.

Metal aquo ions occupy central roles in all equilibria that define metal complexation in natural environments. These complexes are used to establish thermodynamic metrics (i.e., stability constants) for predicting metal binding, which are essential for defining critical parameters associated with aqueous speciation, metal chelation, in vivo transport, and so on. As such, establishing the fundamental chemistry of the actinium(III) aquo ion (Ac-aquo ion, Ac(H 2O) x 3+) is critical for current efforts to develop 225Ac [t 1/2 = 10.0(1) d] as a targeted anticancer therapeutic agent. However, given the limited amount of actinium available for study and its high radioactivity,more » many aspects of actinium chemistry remain poorly defined. We overcame these challenges using the longer-lived 227Ac [t 1/2 = 21.772(3) y] isotope and report the first characterization of this fundamentally important Ac-aquo coordination complex. Our X-ray absorption fine structure study revealed 10.9 ± 0.5 water molecules directly coordinated to the Ac III cation with an Ac–O H2O distance of 2.63(1) Å. This experimentally determined distance was consistent with molecular dynamics density functional theory results that showed (over the course of 8 ps) that Ac III was coordinated by 9 water molecules with Ac–O H2O distances ranging from 2.61 to 2.76 Å. Lastly, the data is presented in the context of other actinide(III) and lanthanide(III) aquo ions characterized by XAFS and highlights the uniqueness of the large Ac III coordination numbers and long Ac–O H2O bond distances.« less

Synthesis and Characterization of the Actinium Aquo Ion

DOE PAGES

Ferrier, Maryline G.; Stein, Benjamin W.; Batista, Enrique R.; ...

2017-02-01

Metal aquo ions occupy central roles in all equilibria that define metal complexation in natural environments. These complexes are used to establish thermodynamic metrics (i.e., stability constants) for predicting metal binding, which are essential for defining critical parameters associated with aqueous speciation, metal chelation, in vivo transport, and so on. As such, establishing the fundamental chemistry of the actinium(III) aquo ion (Ac-aquo ion, Ac(H 2O) x 3+) is critical for current efforts to develop 225Ac [t 1/2 = 10.0(1) d] as a targeted anticancer therapeutic agent. However, given the limited amount of actinium available for study and its high radioactivity,more » many aspects of actinium chemistry remain poorly defined. We overcame these challenges using the longer-lived 227Ac [t 1/2 = 21.772(3) y] isotope and report the first characterization of this fundamentally important Ac-aquo coordination complex. Our X-ray absorption fine structure study revealed 10.9 ± 0.5 water molecules directly coordinated to the Ac III cation with an Ac–O H2O distance of 2.63(1) Å. This experimentally determined distance was consistent with molecular dynamics density functional theory results that showed (over the course of 8 ps) that Ac III was coordinated by 9 water molecules with Ac–O H2O distances ranging from 2.61 to 2.76 Å. Lastly, the data is presented in the context of other actinide(III) and lanthanide(III) aquo ions characterized by XAFS and highlights the uniqueness of the large Ac III coordination numbers and long Ac–O H2O bond distances.« less

A structural role for the PHP domain in E. coli DNA polymerase III

PubMed Central

2013-01-01

Background In addition to the core catalytic machinery, bacterial replicative DNA polymerases contain a Polymerase and Histidinol Phosphatase (PHP) domain whose function is not entirely understood. The PHP domains of some bacterial replicases are active metal-dependent nucleases that may play a role in proofreading. In E. coli DNA polymerase III, however, the PHP domain has lost several metal-coordinating residues and is likely to be catalytically inactive. Results Genomic searches show that the loss of metal-coordinating residues in polymerase PHP domains is likely to have coevolved with the presence of a separate proofreading exonuclease that works with the polymerase. Although the E. coli Pol III PHP domain has lost metal-coordinating residues, the structure of the domain has been conserved to a remarkable degree when compared to that of metal-binding PHP domains. This is demonstrated by our ability to restore metal binding with only three point mutations, as confirmed by the metal-bound crystal structure of this mutant determined at 2.9 Å resolution. We also show that Pol III, a large multi-domain protein, unfolds cooperatively and that mutations in the degenerate metal-binding site of the PHP domain decrease the overall stability of Pol III and reduce its activity. Conclusions While the presence of a PHP domain in replicative bacterial polymerases is strictly conserved, its ability to coordinate metals and to perform proofreading exonuclease activity is not, suggesting additional non-enzymatic roles for the domain. Our results show that the PHP domain is a major structural element in Pol III and its integrity modulates both the stability and activity of the polymerase. PMID:23672456

Simultaneous speciation analysis of inorganic arsenic, chromium and selenium in environmental waters by 3-(2-aminoethylamino) propyltrimethoxysilane modified multi-wall carbon nanotubes packed microcolumn solid phase extraction and ICP-MS.

PubMed

Peng, Hanyong; Zhang, Nan; He, Man; Chen, Beibei; Hu, Bin

2015-01-01

Speciation analysis of inorganic arsenic, chromium and selenium in environmental waters is of great significance for the monitoring of environmental pollution. In this work, 3-(2-aminoethylamino) propyltrimethoxysilane (AAPTS) functionalized multi-wall carbon nanotubes (MWCNTs) were synthesized and employed as the adsorbent for simultaneous speciation analysis of inorganic arsenic, chromium and selenium in environmental waters by microcolumn solid-phase extraction (SPE)-inductively coupled plasma mass spectrometry (ICP-MS). It was found that As(V), Cr(VI) and Se(VI) could be selectively adsorbed on the microcolumn packed with AAPTS-MWCNTs adsorbent at pH around 2.2, while As(III), Cr(III) and Se(IV) could not be retained at this pH and passed through the microcolumn directly. Total inorganic arsenic, chromium and selenium was determined after the oxidation of As(III), Cr(III) and Se(IV) to As(V), Cr(VI) and Se(VI) with 10.0 μmol L(-1) KMnO4. The assay of As(III), Cr(III) and Se(IV) was based on subtracting As(V), Cr(VI) and Se(VI) from the total As, Cr and Se, respectively. Under the optimized conditions, the detection limits of 15, 38 and 16 ng L(-1) with the relative standard deviations (RSDs) of 7.4, 2.4 and 6.2% (c=1 µg L(-1), n=7) were obtained for As(V), Cr(VI) and Se(VI), respectively. The developed method was validated by analyzing four Certified Reference Materials, rainwater, Yangtze River and East Lake waters. Copyright © 2014 Elsevier B.V. All rights reserved.

Subversion of plant cellular functions by bacterial type-III effectors: beyond suppression of immunity.

PubMed

Macho, Alberto P

2016-04-01

Most bacterial plant pathogens employ a type-III secretion system to inject type-III effector (T3E) proteins directly inside plant cells. These T3Es manipulate host cellular processes in order to create a permissive niche for bacterial proliferation, allowing development of the disease. An important role of T3Es in plant pathogenic bacteria is the suppression of plant immune responses. However, in recent years, research has uncovered T3E functions different from direct immune suppression, including the modulation of plant hormone signaling, metabolism or organelle function. This insight article discusses T3E functions other than suppression of immunity, which may contribute to the modulation of plant cells in order to promote bacterial survival, nutrient release, and bacterial replication and dissemination. © 2015 The Author. New Phytologist © 2015 New Phytologist Trust.

A DNA biosensor based on gold nanoparticle decorated on carboxylated multi-walled carbon nanotubes for gender determination of Arowana fish.

PubMed

Saeedfar, Kasra; Heng, Lee Yook; Chiang, Chew Poh

2017-12-01

Multi-wall carbon nanotubes (MWCNTs) were modified to design a new DNA biosensor. Functionalized MWCNTs were equipped with gold nanoparticles (GNPs) (~15nm) (GNP-MWCNTCOOH) to construct DNA biosensors based on carbon-paste screen-printed (SPE) electrodes. GNP attachment onto functionalized MWCNTs was carried out by microwave irradiation and was confirmed by spectroscopic studies and surface analysis. DNA biosensors based on differential pulse voltammetry (DPV) were constructed by immobilizing thiolated single-stranded DNA probes onto GNP-MWCNTCOOH. Ruthenium (III) chloride hexaammoniate [Ru(NH 3 ) 6 ,2Cl - ] (RuHex) was used as hybridization redox indicator. RuHex and MWCNT interaction was low in compared to other organic redox hybridization indicators. The linear response range for DNA determination was 1×10 -21 to 1×10 -9 M with a lower detection limit of 1.55×10 -21 M. Thus, the attachment of GNPs onto functionalized MWCNTs yielded sensitive DNA biosensor with low detection limit and stability more than 30days. Constructed electrode was used to determine gender of arowana fish. Copyright © 2017 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Daugherty, Ashley B.; Horton, John R.; Cheng, Xiaodong

Circular permutation of the NADPH-dependent oxidoreductase Old Yellow Enzyme from Saccharomyces pastorianus (OYE1) can significantly enhance the enzyme’s catalytic performance. Termini relocation into four regions of the protein (sectors I–IV) near the active site has proven effective in altering enzyme function. To better understand the structural consequences and rationalize the observed functional gains in these OYE1 variants, we selected representatives from sectors I–III for further characterization by biophysical methods and X-ray crystallography. These investigations not only show trends in enzyme stability and quaternary structure as a function of termini location but also provide a possible explanation for the catalytic gainsmore » in our top-performing OYE variant (new N-terminus at residue 303; sector III). Crystallographic analysis indicates that termini relocation into sector III affects the loop β6 region (amino acid positions: 290–310) of OYE1, which forms a lid over the active site. Peptide backbone cleavage greatly enhances local flexibility, effectively converting the loop into a tether and consequently increasing the environmental exposure of the active site. Interestingly, such an active site remodeling does not negatively impact the enzyme’s activity and stereoselectivity; neither does it perturb the conformation of other key active site residues with the exception of Y375. These observations were confirmed in truncation experiments, deleting all residues of the loop β6 region in our OYE variant. Intrigued by the finding that circular permutation leaves most of the key catalytic residues unchanged, we also tested OYE permutants for possible additive or synergistic effects of amino acid substitutions. Distinct functional changes in these OYE variants were detected upon mutations at W116, known in native OYE1 to cause inversion of diastereoselectivity for (S)-carvone reduction. In conclusion, our findings demonstrate the contribution of loop β6 toward determining the stereoselectivity of OYE1, an important insight for future OYE engineering efforts.« less

Visual detection and sequential injection determination of aluminium using a cinnamoyl derivative.

PubMed

Elečková, Lenka; Alexovič, Michal; Kuchár, Juraj; Balogh, Ioseph S; Andruch, Vasil

2015-02-01

A cinnamoyl derivative, 3-[4-(dimethylamino)cinnamoyl]-4-hydroxy-6-methyl-3,4-2H-pyran-2-one, was used as a ligand for the determination of aluminium. Upon the addition of an acetonitrile solution of the ligand to an aqueous solution containing Al(III) and a buffer solution at pH 8, a marked change in colour from yellow to orange is observed. The colour intensity is proportional to the concentration of Al(III); thus, the 'naked-eye' detection of aluminium is possible. The reaction is also applied for sequential injection determination of aluminium. Beer׳s law is obeyed in the range from 0.055 to 0.66 mg L(-1) of Al(III). The limit of detection, calculated as three times the standard deviation of the blank test (n=10), was found to be 4 μg L(-1) for Al(III). The method was applied for the determination of aluminium in spiked water samples and pharmaceutical preparations. Copyright © 2014 Elsevier B.V. All rights reserved.

SHINE, The SpHere INfrared survey for Exoplanets

NASA Astrophysics Data System (ADS)

Chauvin, G.; Desidera, S.; Lagrange, A.-M.; Vigan, A.; Feldt, M.; Gratton, R.; Langlois, M.; Cheetham, A.; Bonnefoy, M.; Meyer, M.

2017-12-01

The SHINE survey for SPHERE High-contrast ImagiNg survey for Exoplanets, is a large near-infrared survey of 400-600 young, nearby stars and represents a significant component of the SPHERE consortium Guaranteed Time Observations consisting in 200 observing nights. The scientific goals are: i) to characterize known planetary systems (architecture, orbit, stability, luminosity, atmosphere); ii) to search for new planetary systems using SPHERE's unprecedented performance; and finally iii) to determine the occurrence and orbital and mass function properties of the wide-orbit, giant planet population as a function of the stellar host mass and age. Combined, the results will increase our understanding of planetary atmospheric physics and the processes of planetary formation and evolution.

Developing Novel Protein-based Materials using Ultrabithorax: Production, Characterization, and Functionalization

NASA Astrophysics Data System (ADS)

Huang, Zhao

2011-12-01

Compared to 'conventional' materials made from metal, glass, or ceramics, protein-based materials have unique mechanical properties. Furthermore, the morphology, mechanical properties, and functionality of protein-based materials may be optimized via sequence engineering for use in a variety of applications, including textile materials, biosensors, and tissue engineering scaffolds. The development of recombinant DNA technology has enabled the production and engineering of protein-based materials ex vivo. However, harsh production conditions can compromise the mechanical properties of protein-based materials and diminish their ability to incorporate functional proteins. Developing a new generation of protein-based materials is crucial to (i) improve materials assembly conditions, (ii) create novel mechanical properties, and (iii) expand the capacity to carry functional protein/peptide sequences. This thesis describes development of novel protein-based materials using Ultrabithorax, a member of the Hox family of proteins that regulate developmental pathways in Drosophila melanogaster. The experiments presented (i) establish the conditions required for the assembly of Ubx-based materials, (ii) generate a wide range of Ubx morphologies, (iii) examine the mechanical properties of Ubx fibers, (iv) incorporate protein functions to Ubx-based materials via gene fusion, (v) pattern protein functions within the Ubx materials, and (vi) examine the biocompatibility of Ubx materials in vitro. Ubx-based materials assemble at mild conditions compatible with protein folding and activity, which enables Ubx chimeric materials to retain the function of appended proteins in spatial patterns determined by materials assembly. Ubx-based materials also display mechanical properties comparable to existing protein-based materials and demonstrate good biocompatibility with living cells in vitro. Taken together, this research demonstrates the unique features and future potential of novel Ubx-based materials.

40 CFR 63.304 - Standards for compliance date extension.

Code of Federal Regulations, 2011 CFR

2011-07-01

...) 0.83 percent leaking topside port lids, as determined by the procedures in § 63.309(d)(1); (iii) 4.2... this section, as determined by the procedures in § 63.309(d)(1); (ii) 0.4 percent leaking topside port...) 0.4 percent leaking topside port lids, as determined by the procedures in § 63.309(d)(1); (iii) 2.5...

40 CFR 63.304 - Standards for compliance date extension.

Code of Federal Regulations, 2010 CFR

2010-07-01

...) 0.83 percent leaking topside port lids, as determined by the procedures in § 63.309(d)(1); (iii) 4.2... this section, as determined by the procedures in § 63.309(d)(1); (ii) 0.4 percent leaking topside port...) 0.4 percent leaking topside port lids, as determined by the procedures in § 63.309(d)(1); (iii) 2.5...

Homogeneous and Heterogeneous (Fex, Cr1-x)(OH)3 Precipitation: Implications for Cr Sequestration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dai, Chong; Zuo, Xiaobing; Cao, B

2016-02-16

The formation of (Fe, Cr)(OH)3 nanoparticles determines the fate of aqueous Cr in many aquatic environments. Using small angle X-ray scattering, precipitation rates of (Fe, Cr)(OH)3 nanoparticles in solution and on quartz were quantified from 0.1 mM Fe(III) solutions containing 0 – 0.25 mM Cr(III) at pH = 3.7 ± 0.2. Concentration ratio of aqueous Cr(III)/Fe(III) controlled the chemical composition (x) of (Fex, Cr1-x)(OH)3 precipitates, solutions’ supersaturation with respect to precipitates, and the surface charge of quartz. Therefore, aqueous Cr(III)/Fe(III) ratio affected homogeneous (in solution) and heterogeneous (on quartz) precipitation rates of (Fex, Cr1-x)(OH)3 through different mechanisms. The sequestration mechanismsmore » of Cr(III) in precipitates were also investigated. In solutions with high aqueous Cr(III)/Fe(III) ratios, surface enrichment of Cr(III) on the precipitates occurred, resulting in slower particle growth in solution. From solutions with 0 – 0.1 mM Cr(III), the particles on quartz grew from 2 to 4 nm within 1 h. Interestingly, from solution with 0.25 mM Cr(III), particles of two distinct sizes (2 and 6 nm) formed on quartz, and their sizes remained unchanged throughout the reaction. Our study provided new insights on homogeneous and heterogeneous precipitation of (Fex, Cr1-x)(OH)3 nanoparticles, which can help determine the fate of Cr in aquatic environments.« less

Removal of Arsenic from water using synthetic Fe7S8 nanoparticles

PubMed Central

Cantu, Jesus; Gonzalez, Louis E.; Goodship, Jacqueline; Contreras, Monica; Joseph, Meera; Garza, Cameron; Eubanks, T.M.; Parsons, J.G.

2016-01-01

In the present study, pyrrhotite was used to remove arsenite and arsenate from aqueous solutions. The Fe7S8 was synthesized using a solvothermal synthetic method and it was characterized using XRD and SEM micrographs. Furthermore, the particle size for the nanomaterial Fe7S8 was determined to be 29.86 ± 0.87 nm using Scherer’s equation. During the pH profile studies, the optimum pH for the binding of As (III) and As (V) was determined to be pH 4. Batch isotherm studies were performed to determine the binding capacity of As(III) and As(V), which was determined to be 14.3 mg/g and 31.3 mg/g respectively for 25°C. The thermodynamic studies indicated that the ΔG for the sorption of As(III) and As(V) ranged from −115.5 to −0.96 kJ/mol, indicating a spontaneous process was occurring. The enthalpy indicated that an exothermic reaction was occurring during the adsorption in which the ΔH was −53.69 kJ/mol and −32.51 kJ/mol for As(III) and As(V) respectively. In addition, ΔS values for the reaction had negative values of −160.46 J/K and −99.77 J/K for the adsorption of As(III) and As(V) respectively which indicated that the reaction was spontaneous at low temperatures. Furthermore, the sorption for As(III) and As(V) was determined to follow the second order kinetics adsorption model. PMID:27065750

Cation-Poor Complex Metallic Alloys in Ba(Eu)-Au-Al(Ga) Systems: Identifying the Keys that Control Structural Arrangements and Atom Distributions at the Atomic Level.

PubMed

Smetana, Volodymyr; Steinberg, Simon; Mudryk, Yaroslav; Pecharsky, Vitalij; Miller, Gordon J; Mudring, Anja-Verena

2015-11-02

Four complex intermetallic compounds BaAu(6±x)Ga(6±y) (x = 1, y = 0.9) (I), BaAu(6±x)Al(6±y) (x = 0.9, y = 0.6) (II), EuAu6.2Ga5.8 (III), and EuAu6.1Al5.9 (IV) have been synthesized, and their structures and homogeneity ranges have been determined by single crystal and powder X-ray diffraction. Whereas I and II originate from the NaZn13-type structure (cF104-112, Fm3̅c), III (tP52, P4/nbm) is derived from the tetragonal Ce2Ni17Si9-type, and IV (oP104, Pbcm) crystallizes in a new orthorhombic structure type. Both I and II feature formally anionic networks with completely mixed site occupation by Au and triel (Tr = Al, Ga) atoms, while a successive decrease of local symmetry from the parental structures of I and II to III and, ultimately, to IV correlates with increasing separation of Au and Tr on individual crystallographic sites. Density functional theory-based calculations were employed to determine the crystallographic site preferences of Au and the respective triel element to elucidate reasons for the atom distribution ("coloring scheme"). Chemical bonding analyses for two different "EuAu6Tr6" models reveal maximization of the number of heteroatomic Au-Tr bonds as the driving force for atom organization. The Fermi levels fall in broad pseudogaps for both models allowing some electronic flexibility. Spin-polarized band structure calculations on the "EuAu6Tr6" models hint to singlet ground states for europium and long-range magnetic coupling for both EuAu6.2Ga5.8 (III) and EuAu6.1Al5.9 (IV). This is substantiated by experimental evidence because both compounds show nearly identical magnetic behavior with ferromagnetic transitions at TC = 6 K and net magnetic moments of 7.35 μB/f.u. at 2 K. The effective moments of 8.3 μB/f.u., determined from Curie-Weiss fits, point to divalent oxidation states for europium in both III and IV.

Cation-poor complex metallic alloys in Ba(Eu)–Au–Al(Ga) systems: Identifying the keys that control structural arrangements and atom distributions at the atomic level

DOE PAGES

Smetana, Volodymyr; Steinberg, Simon; Mudryk, Yaroslav; ...

2015-10-19

Four complex intermetallic compounds BaAu 6±xGa 6±y (x = 1, y = 0.9) (I), BaAu 6±xAl 6±y (x = 0.9, y = 0.6) (II), EuAu 6.2Ga 5.8 (III), and EuAu 6.1Al 5.9 (IV) have been synthesized, and their structures and homogeneity ranges have been determined by single crystal and powder X-ray diffraction. Whereas I and II originate from the NaZn 13-type structure (cF104–112, Fm3C), III (tP52, P4/nbm) is derived from the tetragonal Ce 2Ni 17Si 9-type, and IV (oP104, Pbcm) crystallizes in a new orthorhombic structure type. Both I and II feature formally anionic networks with completely mixed site occupationmore » by Au and triel (Tr = Al, Ga) atoms, while a successive decrease of local symmetry from the parental structures of I and II to III and, ultimately, to IV correlates with increasing separation of Au and Tr on individual crystallographic sites. Density functional theory-based calculations were employed to determine the crystallographic site preferences of Au and the respective triel element to elucidate reasons for the atom distribution (“coloring scheme”). Chemical bonding analyses for two different “EuAu 6Tr 6” models reveal maximization of the number of heteroatomic Au–Tr bonds as the driving force for atom organization. The Fermi levels fall in broad pseudogaps for both models allowing some electronic flexibility. Spin-polarized band structure calculations on the “EuAu 6Tr 6” models hint to singlet ground states for europium and long-range magnetic coupling for both EuAu 6.2Ga 5.8 (III) and EuAu 6.1Al 5.9 (IV). This is substantiated by experimental evidence because both compounds show nearly identical magnetic behavior with ferromagnetic transitions at T C = 6 K and net magnetic moments of 7.35 μB/f.u. at 2 K. As a result, the effective moments of 8.3 μB/f.u., determined from Curie–Weiss fits, point to divalent oxidation states for europium in both III and IV.« less

As(III) oxidation by active chlorine and subsequent removal of As(V) by Al13 polymer coagulation using a novel dual function reagent.

PubMed

Hu, Chengzhi; Liu, Huijuan; Chen, Guixia; Jefferson, William A; Qu, Jiuhui

2012-06-19

An electrochemically prepared water treatment reagent containing a high concentration of Al(13) polymer and active chlorine (PACC) showed promising potential for the removal of As(III) due to the combined function of oxidation and coagulation. The results indicated that PACC was effective for As(III) removal through oxidation by the active chlorine and subsequent removal of As(V) by coagulation with the Al(13) polymer. The As(III) was oxidized to As(V) by active chlorine in PACC, with a stoichiometric rate of 0.99 mg Cl(2)/mg As(III). The Al(13) polymer was the most active Al species responsible for As(V) removal in PACC. To meet As drinking water standards the stoichiometric weight ratio of Cl(2)/Al within PACC was 0.09 for the treatment of As(III). Considering the process of As(III) oxidation and As(V) coagulation together, the optimal pH conditions for the removal of As by PACC was within the neutral range, which facilitated the reaction of As(III) with active chlorine and favored the formation of Al hydroxide flocs. The presence of humic acid reduced the As(III) removal efficiency of PACC due to its negative influence on subsequent As(V) coagulation, and disinfection byproduct yields were very low in the presence of insufficient or stoichiometric active chlorine.

Selective removal of cesium from aqueous solutions with nickel (II) hexacyanoferrate (III) functionalized agricultural residue-walnut shell.

PubMed

Ding, Dahu; Lei, Zhongfang; Yang, Yingnan; Feng, Chuanping; Zhang, Zhenya

2014-04-15

A novel nickel (II) hexacyanoferrate (III) functionalized agricultural residue-walnut shell (Ni(II)HCF(III)-WS) was developed to selectively remove cesium ion (Cs(+)) from aqueous solutions. This paper showed the first integral study on Cs(+) removal behavior and waste reduction analysis by using biomass adsorption material. The results indicated that the removal process was rapid and reached saturation within 2h. As a special characteristic of Ni(II)HCF(III)-WS, acidic condition was preferred for Cs(+) removal, which was useful for extending the application scope of the prepared biomass material in treating acidic radioactive liquid waste. The newly developed Ni(II)HCF(III)-WS could selectively remove Cs(+) though the coexisting ions (Na(+) and K(+) in this study) exhibited negative effects. In addition, approximately 99.8% (in volume) of the liquid waste was reduced by using Ni(II)HCF(III)-WS and furthermore 91.9% (in volume) of the spent biomass material (Cs-Ni(II)HCF(III)-WS) was reduced after incineration (at 500°C for 2h). Due to its relatively high distribution coefficient and significant volume reduction, Ni(II)HCF(III)-WS is expected to be a promising material for Cs(+) removal in practice. Copyright © 2014 Elsevier B.V. All rights reserved.

A novel technique to determine cobalt exchangeability in soils using isotope dilution.

PubMed

Wendling, Laura A; Kirby, Jason K; McLaughlin, Michael J

2008-01-01

The environmental risk posed by Co contamination is largely a function of its oxidation state. Our objective was to assess the potential biological availability of Co and the reactions and fate of soluble Co(II) after addition to soils with varying physical and chemical characteristics. A potential risk in quantifying exchangeable Co in soils using isotope dilution techniques is the possible presence of two species of Co in soil solution and adsorbed on soil solid phases [Co(II) and Co(III)], coupled with the possibility that when an isotope of Co is added it may undergo a change in oxidation state during the measurement phase. In this study, we have utilized an isotope dilution technique with cation exchange and high-performance liquid chromatography-inductively coupled plasma-mass spectrometry to determine the isotopically exchangeable Co fraction in several soils with varying characteristics such as differing Al, Fe, and Mn oxide content; pH; and organic carbon content. The application of the cation exchange procedure adjusts measurements of isotopically exchangeable Co to correct for the presence of non-exchangeable 57Co not in equilibrium with the solution phase. Results indicated that oxidation of added 57Co(II) to 57Co(III) or precipitation of 57Co(II) may occur on the surfaces of some soils, particularly those with a high pH or substantial quantities of Mn oxide minerals. No detectable Co(III)(aq) was found in the aqueous extracts of the soils examined.

Golden Proportion Analysis of Dental-Skeletal Patterns of Class II and III Patients Pre and Post Orthodontic-orthognathic Treatment.

PubMed

Bragatto, Fernanda P; Chicarelli, Mariliani; Kasuya, Amanda Vb; Takeshita, Wilton M; Iwaki-Filho, Liogi; Iwaki, Lilian Cv

2016-09-01

The golden proportion has been used in dentistry in an attempt to improve facial function and, possibly, esthetics by simplifying the diagnosis of facial and dental disharmony. The aim of this study is to analyze pre- and postoperative cephalometric tracings of lateral cephalograms of patients with class II and III deformities submitted to orthognathic surgery, and verify if the 13 dental-skeletal patterns (ratios), as defined by Ricketts, moved closer to or further away from the golden proportion. A total of 110 lateral cephalometric radiographs, 55 obtained preoperatively and 55 postoperatively, were analyzed using Dolphin Imaging software. Radiographs analysis demonstrated that ratios 1, 3, 4, 5, 7, 8, 9, 10, and 13 remained statistically different from the golden proportion postoperatively. Ratio 12 was the only one to move closer to the golden number, while the opposite happened with ratio 6, which moved further away after the surgery. Ratios 2 and 11 kept statistically similar to the golden proportion both pre and postoperatively. It may be concluded that orthognathic surgery had little effect on the proportions studied, and that the golden proportion was not present in the majority of the ratios analyzed neither before nor after surgery. Determine whether the facial patterns approach the golden ratio after surgical correction. Also determine whether the golden ratio may be a standard to guide the surgical treatment of patients with skeletal patterns of type II and III.

Saturation kinetics in phenolic O-H bond oxidation by a mononuclear Mn(III)-OH complex derived from dioxygen.

PubMed

Wijeratne, Gayan B; Corzine, Briana; Day, Victor W; Jackson, Timothy A

2014-07-21

The mononuclear hydroxomanganese(III) complex, [Mn(III)(OH)(dpaq)](+), which is supported by the amide-containing N5 ligand dpaq (dpaq = 2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate) was generated by treatment of the manganese(II) species, [Mn(II)(dpaq)](OTf), with dioxygen in acetonitrile solution at 25 °C. This oxygenation reaction proceeds with essentially quantitative yield (greater than 98% isolated yield) and represents a rare example of an O2-mediated oxidation of a manganese(II) complex to generate a single product. The X-ray diffraction structure of [Mn(III)(OH)(dpaq)](+) reveals a short Mn-OH distance of 1.806(13) Å, with the hydroxo moiety trans to the amide function of the dpaq ligand. No shielding of the hydroxo group is observed in the solid-state structure. Nonetheless, [Mn(III)(OH)(dpaq)](+) is remarkably stable, decreasing in concentration by only 10% when stored in MeCN at 25 °C for 1 week. The [Mn(III)(OH)(dpaq)](+) complex participates in proton-coupled electron transfer reactions with substrates with relatively weak O-H and C-H bonds. For example, [Mn(III)(OH)(dpaq)](+) oxidizes TEMPOH (TEMPOH = 2,2'-6,6'-tetramethylpiperidine-1-ol), which has a bond dissociation free energy (BDFE) of 66.5 kcal/mol, in MeCN at 25 °C. The hydrogen/deuterium kinetic isotope effect of 1.8 observed for this reaction implies a concerted proton-electron transfer pathway. The [Mn(III)(OH)(dpaq)](+) complex also oxidizes xanthene (C-H BDFE of 73.3 kcal/mol in dimethylsulfoxide) and phenols, such as 2,4,6-tri-t-butylphenol, with BDFEs of less than 79 kcal/mol. Saturation kinetics were observed for phenol oxidation, implying an initial equilibrium prior to the rate-determining step. On the basis of a collective body of evidence, the equilibrium step is attributed to the formation of a hydrogen-bonding complex between [Mn(III)(OH)(dpaq)](+) and the phenol substrates.

Stochastic Gain Degradation in III-V Heterojunction Bipolar Transistors due to Single Particle Displacement Damage

DOE PAGES

Vizkelethy, Gyorgy; Bielejec, Edward S.; Aguirre, Brandon A.

2017-11-13

As device dimensions decrease single displacement effects are becoming more important. We measured the gain degradation in III-V Heterojunction Bipolar Transistors due to single particles using a heavy ion microbeam. Two devices with different sizes were irradiated with various ion species ranging from oxygen to gold to study the effect of the irradiation ion mass on the gain change. From the single steps in the inverse gain (which is proportional to the number of defects) we calculated Cumulative Distribution Functions to help determine design margins. The displacement process was modeled using the Marlowe Binary Collision Approximation (BCA) code. The entiremore » structure of the device was modeled and the defects in the base-emitter junction were counted to be compared to the experimental results. While we found good agreement for the large device, we had to modify our model to reach reasonable agreement for the small device.« less

Mutation of domain III and domain VI in L gene conserved domain of Nipah virus

NASA Astrophysics Data System (ADS)

Jalani, Siti Aishah; Ibrahim, Nazlina

2016-11-01

Nipah virus (NiV) is the etiologic agent responsible for the respiratory illness and causes fatal encephalitis in human. NiV L protein subunit is thought to be responsible for the majority of enzymatic activities involved in viral transcription and replication. The L protein which is the viral RNA dependent RNA polymerase has high sequence homology among negative sense RNA viruses. In negative stranded RNA viruses, based on sequence alignment six conserved domain (domain I-IV) have been determined. Each domain is separated on variable regions that suggest the structure to consist concatenated functional domain. To directly address the roles of domains III and VI, site-directed mutations were constructed by the substitution of bases at sequences 2497, 2500, 5528 and 5532. Each mutated L gene can be used in future studies to test the ability for expression on in vitro translation.

Detection of human Dicer and Argonaute 2 catalytic activity

PubMed Central

Perron, Marjorie P.; Landry, Patricia; Plante, Isabelle; Provost, Patrick

2013-01-01

The microRNA (miRNA)-guided RNA silencing pathway is a central and well-defined cellular process involved in messenger RNA (mRNA) translational control. This complex regulatory process is achieved by a well orchestrated machinery composed of a relatively few protein components, among which the ribonuclease III (RNase III) Dicer and Argonaute 2 (Ago2) play a central role. These two proteins are essential and it is of particular interest to measure and detect their catalytic activity under various situations and/or conditions. In this chapter, we describe different protocols that aim to study and determine the catalytic activity of Dicer and Ago2 in cell extracts, immune complexes and size-fractionated cell extracts. Another protocol aimed at assessing miRNA binding to Ago2 is also described. These experimental approaches are likely to be useful to researchers investigating the main steps of miRNA biogenesis and function in human health and diseases. PMID:21528451

Stochastic Gain Degradation in III-V Heterojunction Bipolar Transistors due to Single Particle Displacement Damage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vizkelethy, Gyorgy; Bielejec, Edward S.; Aguirre, Brandon A.

As device dimensions decrease single displacement effects are becoming more important. We measured the gain degradation in III-V Heterojunction Bipolar Transistors due to single particles using a heavy ion microbeam. Two devices with different sizes were irradiated with various ion species ranging from oxygen to gold to study the effect of the irradiation ion mass on the gain change. From the single steps in the inverse gain (which is proportional to the number of defects) we calculated Cumulative Distribution Functions to help determine design margins. The displacement process was modeled using the Marlowe Binary Collision Approximation (BCA) code. The entiremore » structure of the device was modeled and the defects in the base-emitter junction were counted to be compared to the experimental results. While we found good agreement for the large device, we had to modify our model to reach reasonable agreement for the small device.« less

[Total oxidative status of peritoneal fluid in women with endometriosis].

PubMed

Polak, Grzegorz; Kotarski, Jan

2010-12-01

Pathophysiology of endometriosis remains enigmatic despite extensive investigations. Accumulating data suggest that oxidative stress in the peritoneal cavity may be implicated in the pathogenesis of endometriosis. The aim of our study was to evaluate the oxidative status of peritoneal fluid (PF) in women with and without endometriosis. Sixty-five women participated in the study 40 women with endometriosis constituted the study group and 25 patients with functional follicle ovarian cysts comprised the reference group. Total oxidative status of PF was determined using a commercially available colorimetric assay kit (Immundiagnostic AG, Cat. nr. KC5100). Women with endometriosis had significantly higher PF oxidative status compared to women with follicle ovarian cysts. No significant difference in the peritoneal oxidative status was found between patients with stage I/II endometriosis, and women with stage III/IV endometriotic disease. Disrupted oxidative status in the peritoneal cavity of women with endometriosis plays a role in the pathogenesis of the disease.

Redox reactions of V(III) and Cr(III)picolinate complexes in aqueous solutions

NASA Astrophysics Data System (ADS)

Vinayakumar, C. K.; Dey, G. R.; Kishore, K.; Moorthy, P. N.

1996-12-01

Reactions of e aq-, H-atoms, OH, (CH 3) 2COH, and CO 2- radicals with V(III)picolinate and Cr(III)picolinate have been studied by the pulse radiolysis technique. The spectra of V(II)picolinate, V(IV)picolinate, Cr(II)picolinate, OH adduct of Cr(III)picolinate and Cr(IV)picolinate have been obtained and the rate constants of the reactions of various radicals with V(III) and Cr(III)picolinate have been determined. The implications of these results to the chemical decontamination of nuclear reactor systems are discussed.

Study of As(III) and As(V) Oxoanion Adsorption onto Single and Mixed Ferrite and Hausmannite Nanomaterials

PubMed Central

Garcia, Sandra; Sardar, Saima; Maldonado, Stephanie; Garcia, Velia; Tamez, C.; Parsons, J. G.

2014-01-01

The removal of arsenic(III) and arsenic(V) from an aqueous solution through adsorption on to Fe3O4, MnFe2O4, 50% Mn substituted Fe3O4, 75% Mn substituted Fe3O4, and Mn3O4 nanomaterials was investigated. Characterization of the nanomaterials using XRD showed only pure phases for Mn3O4, MnFe2O4, and Fe3O4. The 50% and 75% substituted nanomaterials were found to be mixtures of Mn3O4 and Fe3O4. From batch studies the optimum binding pH of arsenic(III) and arsenic(V) to the nanomaterials was determined to be pH 3. The binding capacity for As(III) and As(VI) to the various nanomaterials was determined using Isotherm studies. The binding capacity of Fe3O4 was determined to be 17.1 mg/g for arsenic(III) and 7.0 mg/g for arsenic(V). The substitution of 25% Mn into the Fe3O4 lattice showed a slight increase in the binding capacity for As(III) and As(VI) to 23.8 mg/g and 7.9 mg/g, respectively. The 50% substituted showed the maximum binding capacity of 41.5 mg/g and 13.9 mg/g for arsenic(III) and arsenic(V). The 75% Mn substituted Fe3O4 capacities were 16.7 mg/g for arsenic(III) and 8.2 mg/g for arsenic(V). The binding capacity of the Mn3O4 was determined to be 13.5 mg/g for arsenic(III) and 7.5 mg/g for arsenic(V). In addition, interference studies on the effects of SO2−4, PO3−4, Cl−, and NO−3 investigated. All the interferences had very minimal effects on the As(III) and As(V) binding never fell below 20% even in the presence of 1000 ppm interfering ions. PMID:25097269

Applications of Displacement Transfer Functions to Deformed Shape Predictions of the G-III Swept-Wing Structure

NASA Technical Reports Server (NTRS)

Lung, Shun-Fat; Ko, William L.

2016-01-01

In support of the Adaptive Compliant Trailing Edge [ACTE] project at the NASA Armstrong Flight Research Center, displacement transfer functions were applied to the swept wing of a Gulfstream G-III airplane (Gulfstream Aerospace Corporation, Savannah, Georgia) to obtain deformed shape predictions. Four strainsensing lines (two on the lower surface, two on the upper surface) were used to calculate the deformed shape of the G III wing under bending and torsion. There being an insufficient number of surface strain sensors, the existing G III wing box finite element model was used to generate simulated surface strains for input to the displacement transfer functions. The resulting predicted deflections have good correlation with the finite-element generated deflections as well as the measured deflections from the ground load calibration test. The convergence study showed that the displacement prediction error at the G III wing tip can be reduced by increasing the number of strain stations (for each strain-sensing line) down to a minimum error of l.6 percent at 17 strain stations; using more than 17 strain stations yielded no benefit because the error slightly increased to 1.9% when 32 strain stations were used.

Americium(III) capture using phosphonic acid-functionalized silicas with different mesoporous morphologies: adsorption behavior study and mechanism investigation by EXAFS/XPS.

PubMed

Zhang, Wen; He, Xihong; Ye, Gang; Yi, Rong; Chen, Jing

2014-06-17

Efficient capture of highly toxic radionuclides with long half-lives such as Americium-241 is crucial to prevent radionuclides from diffusing into the biosphere. To reach this purpose, three different types of mesoporous silicas functionalized with phosphonic acid ligands (SBA-POH, MCM-POH, and BPMO-POH) were synthesized via a facile procedure. The structure, surface chemistry, and micromorphology of the materials were fully characterized by (31)P/(13)C/(29)Si MAS NMR, XPS, and XRD analysis. Efficient adsorption of Am(III) was realized with a fast rate to reach equilibrium (within 10 min). Influences including structural parameters and functionalization degree on the adsorption behavior were investigated. Slope analysis of the equilibrium data suggested that the coordination with Am(III) involved the exchange of three protons. Moreover, extended X-ray absorption fine structure (EXAFS) analysis, in combination with XPS survey, was employed for an in-depth probe into the binding mechanism by using Eu(III) as a simulant due to its similar coordination behavior and benign property. The results showed three phosphonic acid ligands were coordinated to Eu(III) in bidentate fashion, and Eu(P(O)O)3(H2O) species were formed with the Eu-O coordination number of 7. These phosphonic acid-functionalized mesoporous silicas should be promising for the treatment of Am-containing radioactive liquid waste.

Covalency in lanthanides. An X-ray absorption spectroscopy and density functional theory study of LnCl6(x-) (x = 3, 2).

PubMed

Löble, Matthias W; Keith, Jason M; Altman, Alison B; Stieber, S Chantal E; Batista, Enrique R; Boland, Kevin S; Conradson, Steven D; Clark, David L; Lezama Pacheco, Juan; Kozimor, Stosh A; Martin, Richard L; Minasian, Stefan G; Olson, Angela C; Scott, Brian L; Shuh, David K; Tyliszczak, Tolek; Wilkerson, Marianne P; Zehnder, Ralph A

2015-02-25

Covalency in Ln-Cl bonds of Oh-LnCl6(x-) (x = 3 for Ln = Ce(III), Nd(III), Sm(III), Eu(III), Gd(III); x = 2 for Ln = Ce(IV)) anions has been investigated, primarily using Cl K-edge X-ray absorption spectroscopy (XAS) and time-dependent density functional theory (TDDFT); however, Ce L3,2-edge and M5,4-edge XAS were also used to characterize CeCl6(x-) (x = 2, 3). The M5,4-edge XAS spectra were modeled using configuration interaction calculations. The results were evaluated as a function of (1) the lanthanide (Ln) metal identity, which was varied across the series from Ce to Gd, and (2) the Ln oxidation state (when practical, i.e., formally Ce(III) and Ce(IV)). Pronounced mixing between the Cl 3p- and Ln 5d-orbitals (t2g* and eg*) was observed. Experimental results indicated that Ln 5d-orbital mixing decreased when moving across the lanthanide series. In contrast, oxidizing Ce(III) to Ce(IV) had little effect on Cl 3p and Ce 5d-orbital mixing. For LnCl6(3-) (formally Ln(III)), the 4f-orbitals participated only marginally in covalent bonding, which was consistent with historical descriptions. Surprisingly, there was a marked increase in Cl 3p- and Ce(IV) 4f-orbital mixing (t1u* + t2u*) in CeCl6(2-). This unexpected 4f- and 5d-orbital participation in covalent bonding is presented in the context of recent studies on both tetravalent transition metal and actinide hexahalides, MCl6(2-) (M = Ti, Zr, Hf, U).

On-line determination of Sb(III) and total Sb using baker's yeast immobilized on polyurethane foam and hydride generation inductively coupled plasma optical emission spectrometry

NASA Astrophysics Data System (ADS)

Menegário, Amauri A.; Silva, Ariovaldo José; Pozzi, Eloísa; Durrant, Steven F.; Abreu, Cassio H.

2006-09-01

The yeast Saccharomyces cerevisiae was immobilized in cubes of polyurethane foam and the ability of this immobilized material to separate Sb(III) and Sb(V) was investigated. A method based on sequential determination of total Sb (after on-line reduction of Sb(V) to Sb(III) with thiourea) and Sb(III) (after on-line solid-liquid phase extraction) by hydride generation inductively coupled plasma optical emission spectrometry is proposed. A flow system assembled with solenoid valves was used to manage all stages of the process. The effects of pH, sample loading and elution flow rates on solid-liquid phase extraction of Sb(III) were evaluated. Also, the parameters related to on-line pre-reduction (reaction coil and flow rates) were optimized. Detection limits of 0.8 and 0.15 μg L - 1 were obtained for total Sb and Sb(III), respectively. The proposed method was applied to the analysis of river water and effluent samples. The results obtained for the determination of total Sb were in agreement with expected values, including the river water Standard Reference Material 1640 certified by the National Institute of Standards and Technology (NIST). Recoveries of Sb(III) and Sb(V) in spiked samples were between 81 ± 19 and 111 ±15% when 120 s of sample loading were used.

Atomic Resolution Structure of the Oncolytic Parvovirus LuIII by Electron Microscopy and 3D Image Reconstruction.

PubMed

Pittman, Nikéa; Misseldine, Adam; Geilen, Lorena; Halder, Sujata; Smith, J Kennon; Kurian, Justin; Chipman, Paul; Janssen, Mandy; Mckenna, Robert; Baker, Timothy S; D'Abramo, Anthony; Cotmore, Susan; Tattersall, Peter; Agbandje-McKenna, Mavis

2017-10-30

LuIII, a protoparvovirus pathogenic to rodents, replicates in human mitotic cells, making it applicable for use to kill cancer cells. This virus group includes H-1 parvovirus (H-1PV) and minute virus of mice (MVM). However, LuIII displays enhanced oncolysis compared to H-1PV and MVM, a phenotype mapped to the major capsid viral protein 2 (VP2). This suggests that within LuIII VP2 are determinants for improved tumor lysis. To investigate this, the structure of the LuIII virus-like-particle was determined using single particle cryo-electron microscopy and image reconstruction to 3.17 Å resolution, and compared to the H-1PV and MVM structures. The LuIII VP2 structure, ordered from residue 37 to 587 (C-terminal), had the conserved VP topology and capsid morphology previously reported for other protoparvoviruses. This includes a core β-barrel and α-helix A, a depression at the icosahedral 2-fold and surrounding the 5-fold axes, and a single protrusion at the 3-fold axes. Comparative analysis identified surface loop differences among LuIII, H-1PV, and MVM at or close to the capsid 2- and 5-fold symmetry axes, and the shoulder of the 3-fold protrusions. The 2-fold differences cluster near the previously identified MVM sialic acid receptor binding pocket, and revealed potential determinants of protoparvovirus tumor tropism.

Quantitative EEG reflects non-dopaminergic disease severity in Parkinson's disease.

PubMed

Geraedts, Victor J; Marinus, Johan; Gouw, Alida A; Mosch, Arne; Stam, Cornelis J; van Hilten, Jacobus J; Contarino, Maria Fiorella; Tannemaat, Martijn R

2018-05-29

In Parkinson's Disease (PD), measures of non-dopaminergic systems involvement may reflect disease severity and therefore contribute to patient-selection for Deep Brain Stimulation (DBS). There is currently no determinant for non-dopaminergic disease severity. In this exploratory study, we investigated whether quantitative EEG reflects non-dopaminergic disease severity in PD. Sixty-three consecutive PD patients screened for DBS were included (mean age 62.4 ± 7.2 years, 32% females). Relative spectral powers and the Phase-Lag-Index (PLI) reflecting functional connectivity were analysed on routine EEGs. Non-dopaminergic disease severity was quantified using the SENS-PD score and its subdomains; motor-severity was quantified using the MDS-UPDRS III. The SENS-PD composite score correlated with a spectral ratio ((δ + θ)/(α1 + α2 + β) powers) (global spectral ratio Pearson's r = 0.4, 95% Confidence Interval (95%CI) 0.1-0.6), and PLI in the α2 band (10-13 Hz) (r = -0.3, 95%CI -0.5 to -0.1). These correlations seem driven by the subdomains cognition and psychotic symptoms. MDS-UPDRS III was not significantly correlated with EEG parameters. EEG slowing and reduced functional connectivity in the α2 band were associated with non-dopaminergic disease severity in PD. The described EEG parameters may have complementary utility as determinants of non-dopaminergic involvement in PD. Copyright © 2018 International Federation of Clinical Neurophysiology. Published by Elsevier B.V. All rights reserved.

Functional outcomes in pediatric severe sepsis: further analysis of the researching severe sepsis and organ dysfunction in children: a global perspective trial.

PubMed

Farris, Reid W D; Weiss, Noel S; Zimmerman, Jerry J

2013-11-01

To evaluate risk factors for poor functional outcome in 28-day survivors after an episode of severe sepsis. Retrospective cohort study examining data from the Researching Severe Sepsis and Organ Dysfunction in Children: A Global Perspective trial (NCT00049764). One hundred and four pediatric centers in 18 countries. Children with severe sepsis who required both vasoactive-inotropic infusions and mechanical ventilation and who survived to 28 days (n = 384). None. Poor functional outcome was defined as a Pediatric Overall Performance Category score greater than or equal to 3 and an increase from baseline when measured 28 days after trial enrollment. Median Pediatric Overall Performance Category at enrollment was 1 (interquartile range, 1-2). Median Pediatric Overall Performance Category at 28 days was 2 (interquartile range, 1-4). Thirty-four percent of survivors had decline in their functional status at 28 days, and 18% were determined to have a "poor" functional outcome. Hispanic ethnicity was associated with poor functional outcome compared to the white referent group (risk ratio = 1.9; 95% CI: 1.0-3.0). Clinical factors associated with increased risk of poor outcome included CNS and intra-abdominal infection sources compared to the lung infection referent category (risk ratio = 3.3; 95% CI: 1.4-5.6 and 2.4; 95% CI: 1.0-4.5, respectively); a history of recent trauma (risk ratio = 3.9; 95% CI: 1.4-5.4); receipt of cardiopulmonary resuscitation prior to enrollment (risk ratio = 5.1; 95% CI: 2.9-5.7); and baseline Pediatric Risk of Mortality III score of 20-29 (risk ratio = 2.8; 95% CI: 1.2-5.2) and Pediatric Risk of Mortality III greater than or equal to 30 (risk ratio = 4.5; 95% CI: 1.6-8.0) compared to the referent group with Pediatric Risk of Mortality III scores of 0-9. In this sample of 28-day survivors of pediatric severe sepsis diminished functional status was common. This analysis provides evidence that particular patient characteristics and aspects of an individual's clinical course are associated with poor functional outcome 28 days after onset of severe sepsis. These characteristics may provide opportunity for intervention in order to improve functional outcome in pediatric patients with severe sepsis. Decline in functional status 28 days after onset of severe sepsis is a frequent and potentially clinically meaningful event. Utilization of functional status as the primary outcome in future pediatric sepsis clinical trials should be considered.

Validity of the language development survey in infants born preterm.

PubMed

Beaulieu-Poulin, Camille; Simard, Marie-Noëlle; Babakissa, Hélène; Lefebvre, Francine; Luu, Thuy Mai

2016-07-01

Preterm infants are at greater risk of language delay. Early identification of language delay is essential to improve functional outcome in these children. To examine the concurrent validity of Rescorla's Language Development Survey and the Bayley Scales of Infant and Toddler Development (Bayley-III) at 18months corrected age in preterm infants. Test accuracy study. 189 preterm infants born <29weeks were assessed at 18months. The Language Development Survey, a parent-reported screening instrument, was administered in French concurrently with the Language Scales of the Bayley-III. Receiver-Operating-Characteristics curves were used to determine optimal cut-off score on the Language Development Survey to identify Bayley-III score <85. Sensitivity, specificity, positive and negative predictive values, and κ coefficient were calculated. Using Rescorla's original cut-off scores of ≤10 words for boys and ≤24 for girls, sensitivity was 76% and 88% for boys and girls, respectively, and specificity was 73% and 52% for boys and girls, respectively, in identifying language delay as per the Bayley-III. The optimal threshold was ≤10 words for both boys and girls. In girls, lowering the cut-off score decreased sensitivity (79%), but improved specificity (82%), thus lowering the number of false-positives. Our findings support using the Language Development Survey as an expressive language screener in preterm infants. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Hydrothermal synthesis, crystal structure, luminescent and magnetic properties of a new mononuclear GdIII coordination complex

NASA Astrophysics Data System (ADS)

Coban, Mustafa Burak

2018-06-01

A new GdIII coordination complex, {[Gd(2-stp)2(H2O)6].2(4,4'-bipy).4(H2O)}, complex 1, (2-stp = 2-sulfoterephthalate anion and 4,4'-bipy = 4,4'-bipyridine), has been synthesized by hydrothermal method and characterized by elemental analysis, solid state UV-Vis and FT-IR spectroscopy, single-crystal X-ray diffraction, solid state photoluminescence and variable-temperature magnetic measurements. The crystal structure determination shows that GdIII ions are eight coordinated and adopt a distorted square-antiprismatic geometry. Molecules interacting through intra- and intermolecular (O-H⋯O, O-H⋯N) hydrogen bonds in complex 1, give rise to 3D hydrogen bonded structure and the discrete lattice 4,4'-bipy molecules occupy the channel of the 3D structure. π-π stacking interactions also exist 4,4'-bipy-4,4'-bipy and 4,4'-bipy-2-stp molecule rings in 3D structures. Additionally, solid state photoluminescence properties of complex 1 at room temperature have been investigated. Under the excitation of UV light (at 349 nm), the complex 1 exhibited green emissions (at 505 nm) of GdIII ion in the visible region. Furthermore, Variable-temperature magnetic susceptibility and isothermal magnetization as function of external magnetic field studies reveal that complex 1 displays possible antiferromagnetic interaction.

Classification of residents in nursing homes in Tuscany (Italy) using Resource Utilization Groups Version III (RUG-III).

PubMed

Francesconi, Paolo; Cantini, Elisabetta; Bavazzano, Emanuela; Lauretani, Fabrizio; Bandinelli, Stefania; Buiatti, Eva; Ferrucci, Luigi

2006-04-01

Samples of nursing homes in Tuscany (Italy) classify their residents and determine their case-mix according to the Resource Utilization Groups System, Version III (RUG-III). A large sample of nursing homes was selected, based on willingness to participate, representation of both public and private institutions, and wide geographic representation. Two registered nurses assessed all residents using the RUG questionnaire. The information collected was then used to group residents into 44 RUGs, and facility-specific case-mix indices were calculated using the RUG-specific weights previously validated in Italy. A total of 3981 residents from 93 nursing homes were assessed. Most residents were over 75 years old (87.4%) and women (68.6%). A large percentage was classified into RUGs within the following primary categories: reduced physical function (33.6%), impaired cognition (17.6%) and clinically complex (17.6%). The resulting nursing home case-mix indices ranged from 0.627 to 1.108 (mean 0.807+/-0.110). No significant association was found between type of facility, level of fees, or extent of staff in the nursing homes and their case-mix indices. RUGIII can provide information on types of nursing home residents and their care needs. This is useful for monitoring and evaluating long-term care services for the elderly, and allows for more effective planning and allocation of staffing and financial resources.

Relativistic many-body calculation of energies, transition rates, lifetimes, and multipole polarizabilities in Cs-like La iii

NASA Astrophysics Data System (ADS)

Safronova, U. I.; Safronova, M. S.

2014-05-01

Excitation energies of the [Xe]nd (n =5-9), [Xe]ns (n =6-10), [Xe]np (n =6-9), [Xe]nf (n =4-8), and [Xe]ng (n =5-8) states in La iii, where [Xe] = 1s22s22p63s23p63d104s24p64d105s25p6, are evaluated. Electric dipole matrix elements for the allowed transitions between the low-lying [Xe]nd, [Xe]ns, [Xe]np, [Xe]nf, and [Xe]ng states in the La iii ion are calculated using the high-precision relativistic all-order method where all single, double, and partial triple excitations of the Dirac-Fock wave functions are included to all orders of perturbation theory. Recommended values are provided for a large number of electric dipole matrix elements, oscillator strengths, transition rates, and lifetimes. Scalar and tensor polarizabilities of the states listed above are evaluated. The uncertainties of the recommended values are estimated. Electric quadrupole and magnetic dipole matrix elements are calculated to determine lifetimes of the 5d5/2 and 6s metastable levels. The ground-state E1, E2, and E3 static polarizabilities are calculated. This work provides recommended values critically evaluated for their accuracy for a number of La iii atomic properties for use in planning and analysis of various experiments as well as theoretical modeling.

Differential determination of chromium(VI) and total chromium in natural waters using flow injection on-line separation and preconcentration electrothermal atomic absorption spectrometry.

PubMed

Sperling, M; Yin, X; Welz, B

1992-03-01

A rapid, sensitive and selective method for the differential determination of CrIII and CrVI in natural waters is described. Chromium(vi) can be determined directly by flow injection on-line sorbent extraction preconcentration coupled with electrothermal atomic absorption spectrometry using sodium diethyldithiocarbamate as the complexing agent and C18 bonded silica reversed-phase sorbent as the column material. Total Cr can be determined after oxidation of CrIII to CrVI by potassium peroxydisulfate. Chromium(III) can be calculated by difference. The optimum conditions for sorbent extraction of CrVI and oxidation of CrIII to CrVI are evaluated. A 12-fold enhancement in sensitivity compared with direct introduction of 40 microliters samples was achieved after preconcentration for 60 s, giving detection limits of 16 ng l-1 for CrVI and 18 ng l-1 for total Cr (based on 3 sigma). Results obtained for sea-water and river water reference materials were all within the certified range for total Cr with a precision of better than 10% relative standard deviation in the range 100-200 ng l-1. The selectivity of the determination of CrVI was evaluated by analysing spiked reference materials in the presence of CrIII, resulting in quantitative recovery of CrVI.

A simple and sensitive fluorimetric aptasensor for the ultrasensitive detection of arsenic(III) based on cysteamine stabilized CdTe/ZnS quantum dots aggregation.

PubMed

Ensafi, Ali A; Kazemifard, N; Rezaei, B

2016-03-15

A new approach for developing a fluorimetric aptasensor has been described and applied for determination of a highly toxic cation, As(III). In this method an aptamer was used to aggregate cationic cysteamine-stabilized CdTe/ZnS core/shell quantum dots, as a result fluorescence quenching was accrued. In the presence of As(III), the aptamer and As(III) make a complex, which prevents aggregation of the quantum dots. Thus, the fluorescence intensity of the quantum dots was enhanced upon the de-aggregation, which depends on the concentration of As(III). The fluorimetric assay has a very low detection limit of 1.3 pmolL(-1) As(III) with a dynamic range of 1.0 × 10(-11) to 1.0 × 10(-6) molL(-1). The interference effect of a wide variety of cations and anions was investigated, and the obtained results confirm high selectivity of the aptasensor for As(III) detection. The present assay was successfully applied for the determination of As(III) in several water samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Global Regulatory Functions of the Staphylococcus aureus Endoribonuclease III in Gene Expression

PubMed Central

Lioliou, Efthimia; Sharma, Cynthia M.; Caldelari, Isabelle; Helfer, Anne-Catherine; Fechter, Pierre; Vandenesch, François; Vogel, Jörg; Romby, Pascale

2012-01-01

RNA turnover plays an important role in both virulence and adaptation to stress in the Gram-positive human pathogen Staphylococcus aureus. However, the molecular players and mechanisms involved in these processes are poorly understood. Here, we explored the functions of S. aureus endoribonuclease III (RNase III), a member of the ubiquitous family of double-strand-specific endoribonucleases. To define genomic transcripts that are bound and processed by RNase III, we performed deep sequencing on cDNA libraries generated from RNAs that were co-immunoprecipitated with wild-type RNase III or two different cleavage-defective mutant variants in vivo. Several newly identified RNase III targets were validated by independent experimental methods. We identified various classes of structured RNAs as RNase III substrates and demonstrated that this enzyme is involved in the maturation of rRNAs and tRNAs, regulates the turnover of mRNAs and non-coding RNAs, and autoregulates its synthesis by cleaving within the coding region of its own mRNA. Moreover, we identified a positive effect of RNase III on protein synthesis based on novel mechanisms. RNase III–mediated cleavage in the 5′ untranslated region (5′UTR) enhanced the stability and translation of cspA mRNA, which encodes the major cold-shock protein. Furthermore, RNase III cleaved overlapping 5′UTRs of divergently transcribed genes to generate leaderless mRNAs, which constitutes a novel way to co-regulate neighboring genes. In agreement with recent findings, low abundance antisense RNAs covering 44% of the annotated genes were captured by co-immunoprecipitation with RNase III mutant proteins. Thus, in addition to gene regulation, RNase III is associated with RNA quality control of pervasive transcription. Overall, this study illustrates the complexity of post-transcriptional regulation mediated by RNase III. PMID:22761586

Spectroscopic characterization and reactivity studies of a mononuclear nonheme Mn(III)-hydroperoxo complex.

PubMed

So, Hee; Park, Young Jun; Cho, Kyung-Bin; Lee, Yong-Min; Seo, Mi Sook; Cho, Jaeheung; Sarangi, Ritimukta; Nam, Wonwoo

2014-09-03

We report the first example of a mononuclear nonheme manganese(III)-hydroperoxo complex derived from protonation of an isolated manganese(III)-peroxo complex bearing an N-tetramethylated cyclam (TMC) ligand, [Mn(III)(TMC)(OOH)](2+). The Mn(III)-hydroperoxo intermediate is characterized with various spectroscopic methods as well as with density functional theory (DFT) calculations, showing the binding of a hydroperoxide ligand in an end-on fashion. The Mn(III)-hydroperoxo species is a competent oxidant in oxygen atom transfer (OAT) reactions, such as the oxidation of sulfides. The electrophilic character of the Mn(III)-hydroperoxo complex is demonstrated unambiguously in the sulfoxidation of para-substituted thioanisoles.

FMAP: Functional Mapping and Analysis Pipeline for metagenomics and metatranscriptomics studies.

PubMed

Kim, Jiwoong; Kim, Min Soo; Koh, Andrew Y; Xie, Yang; Zhan, Xiaowei

2016-10-10

Given the lack of a complete and comprehensive library of microbial reference genomes, determining the functional profile of diverse microbial communities is challenging. The available functional analysis pipelines lack several key features: (i) an integrated alignment tool, (ii) operon-level analysis, and (iii) the ability to process large datasets. Here we introduce our open-sourced, stand-alone functional analysis pipeline for analyzing whole metagenomic and metatranscriptomic sequencing data, FMAP (Functional Mapping and Analysis Pipeline). FMAP performs alignment, gene family abundance calculations, and statistical analysis (three levels of analyses are provided: differentially-abundant genes, operons and pathways). The resulting output can be easily visualized with heatmaps and functional pathway diagrams. FMAP functional predictions are consistent with currently available functional analysis pipelines. FMAP is a comprehensive tool for providing functional analysis of metagenomic/metatranscriptomic sequencing data. With the added features of integrated alignment, operon-level analysis, and the ability to process large datasets, FMAP will be a valuable addition to the currently available functional analysis toolbox. We believe that this software will be of great value to the wider biology and bioinformatics communities.

The Intrinsic Electrophysiological Properties of Mammalian Neurons: Insights into Central Nervous System Function

NASA Astrophysics Data System (ADS)

Llinas, Rodolfo R.

1988-12-01

This article reviews the electroresponsive properties of single neurons in the mammalian central nervous system (CNS). In some of these cells the ionic conductances responsible for their excitability also endow them with autorhythmic electrical oscillatory properties. Chemical or electrical synaptic contacts between these neurons often result in network oscillations. In such networks, autorhytmic neurons may act as true oscillators (as pacemakers) or as resonators (responding preferentially to certain firing frequencies). Oscillations and resonance in the CNS are proposed to have diverse functional roles, such as (i) determining global functional states (for example, sleep-wakefulness or attention), (ii) timing in motor coordination, and (iii) specifying connectivity during development. Also, oscillation, especially in the thalamo-cortical circuits, may be related to certain neurological and psychiatric disorders. This review proposes that the autorhythmic electrical properties of central neurons and their connectivity form the basis for an intrinsic functional coordinate system that provides internal context to sensory input.

All Roads Lead to Rome: Update on Rome III Criteria and New Treatment Options

PubMed Central

Shih, David Q.; Kwan, Lola Y.

2010-01-01

The recently published Rome III criteria reflect current understanding of functional gastrointestinal disorders. These criteria include definitions of these conditions and their pathophysiologic subtypes and offer guidelines for their management. At the 2006 Annual Scientific Meeting of the American College of Gastroenterology, a panel of experts discussed these criteria as they pertain to irritable bowel syndrome, functional dyspepsia, and chronic constipation. This article reviews the panel’s findings, highlights the differences between the Rome II and III criteria, and summarizes best treatment options currently available to practitioners and their patients. PMID:21544252

Structural stability of coprecipitated natural organic matter and ferric iron under reducing conditions

USGS Publications Warehouse

Henneberry, Yumiko K.; Kraus, Tamara E.C.; Nico, Peter S.; Horwath, William R.

2012-01-01

The objective was to assess the interaction of Fe coprecipitated with dissolved organic matter (DOM) and its effect on Fe (hydr)oxide crystallinity and DOM retention under abiotic reducing conditions. A Fe-based coagulant was reacted with DOM from an agricultural drain and the resulting precipitate (floc) was exposed to S(-II) and Fe(II). Solution concentrations of Fe(II/III) and DOM were monitored, floc crystallinity was determined using X-ray diffraction, and the composition and distribution of functional groups were assessed using scanning transmission X-ray microscopy (STXM) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. Results indicate coprecipitation of Fe(III) with DOM forms a non-crystalline floc that withstands crystallization regardless of change in pH, Fe:DOM ratio and type of reductant added. There was no evidence that exposure to reducing conditions led to release of DOM from the floc, indicating that coprecipitation with complex natural DOM in aquatic environments may stabilize Fe (hydr)oxides against crystallization upon reaction with reduced species and lead to long term sequestration of the DOM. STXM analysis identified spatially distinct regions with remarkable functional group purity, contrary to the model of DOM as a relatively uniform complex polymer lacking identifiable organic compounds. Polysaccharide-like OM was strongly and directly correlated with the presence of Fe but showed different Fe binding strength depending on the presence of carboxylic acid functional groups, whereas amide and aromatic functional groups were inversely correlated with Fe content.

Far-infrared line observations of planetary nebulae. 1: The O 3 spectrum

NASA Technical Reports Server (NTRS)

Dinerstein, H. L.; Lester, D. F.; Werner, M. W.

1985-01-01

Observations of the far-infrared fine structure lines of O III have been obtained for six planetary nebulae. The infrared measurements are combined with optical O III line fluxes to probe physical conditions in the gas. From the observed line intensity ratios, a simultaneous solution was obtained for electron temperature and density, as well as means of evaluating the importance of inhomogeneities. Densities determined from the far-infrared O III lines agree well density diagnostics from other ions, indicating a fairly homogeneous density in the emitting gas. Temperatures are determined separately from the O III 4363/5007 A and 5007 A/52 micron intensity ratios and compared. Systematically higher values are derived from the former ratio, which is expected from a nebula which is not isothermal. Allowance for the presence of temperature variations within these nebulae raises their derived oxygen abundances, determinations to be reconciled with the solar value.

Anodic Stripping Voltammetry with Pencil Graphite Electrode for Determination of Chromium (III)

NASA Astrophysics Data System (ADS)

Wyantuti, S.; Hafidza, R. A.; Ishmayana, S.; Hartati, Y. W.

2017-02-01

Chromium is required as micronutrient that has roles in insulin metabolism and blood glucose level regulation. Chromium (III) deficiency can cause hyperglycemia and glycosuria. However, a high amount of chromium in body can cause allergic reaction, organ damage, and even death because of its toxicity. Chromium is commonly used in steel industries. Simultaneously with the development of industry, the waste disposal that can endanger environment also increased. Therefore, a sensitive and specific analysis method for chromium detection is required. Stripping voltammetry is one of the voltammetric methods that is commonly used for heavy metal analysis due to the very low limit of detection (sub ppb). The present study was conducted to develop an analysis method for chromium (III) determination using pencil graphite electrode. Quantitative determination was performed for chromium (III) which measured at -0.8 to +1.0 V with deposition time for 60 s and 50 mV/s scan rate. Stripping voltammetric analysis of chromium (III) using pencil graphite electrode gave linear range at 12.5 to 75 ppm with limit of detection of 0.31 ppm.

Linear scan voltammetric indirect determination of Al(III) by the catalytic cathodic response of norepinephrine at the hanging mercury drop electrode.

PubMed

Zhang, Fuping; Ji, Ming; Xu, Quan; Yang, Li; Bi, Shuping

2005-09-01

The biological effects of aluminum (Al) have received much attention in recent years. Al is of basic relevance as concern with its reactivity and bioavailability. In this paper, the electrochemical behaviors of norepinephrine (NE) in the absence and presence of Al(III) at the hanging mercury drop electrode have been studied and applied to the practical analysis. Highly selective catalytic cathodic peak of NE is yielded by linear scan voltammetry (LSV) at -1.32 V (vs. SCE). A linear relationship holds between the cathodic peak current and the Al(III) concentration. It has been successfully applied to the determination of Al(III) in real waters and synthetic biological samples with satisfying results, which are in accordance with those obtained by ICP-AES method. The electrochemical properties and the mechanisms of the peaks in the presence and absence of Al(III) have been explored. The results show that they are irreversible adsorptive hydrogen catalytic waves. These studies not only enrich the methods of determining Al, but also lay foundations of further understanding of the mechanisms of neurodementia.

A Mechanistic Investigation of the Gold(III)-Catalyzed Hydrofurylation of C-C Multiple Bonds.

PubMed

Hossein Bagi, Amin; Khaledi, Yousef; Ghari, Hossein; Arndt, Sebastian; Hashmi, A Stephen K; Yates, Brian F; Ariafard, Alireza

2016-11-09

The gold-catalyzed direct functionalization of aromatic C-H bonds has attracted interest for constructing organic compounds which have application in pharmaceuticals, agrochemicals, and other important fields. In the literature, two major mechanisms have been proposed for these catalytic reactions: inner-sphere syn-addition and outer-sphere anti-addition (Friedel-Crafts-type mechanism). In this article, the AuCl 3 -catalyzed hydrofurylation of allenyl ketone, vinyl ketone, ketone, and alcohol substrates is investigated with the aid of density functional theory calculations, and it is found that the corresponding functionalizations are best rationalized in terms of a novel mechanism called "concerted electrophilic ipso-substitution" (CEIS) in which the gold(III)-furyl σ-bond produced by furan auration acts as a nucleophile and attacks the protonated substrate via an outer-sphere mechanism. This unprecedented mechanism needs to be considered as an alternative plausible pathway for gold(III)-catalyzed arene functionalization reactions in future studies.

Transdermal rotigotine in early stage Parkinson's disease: a randomized, double-blind, placebo-controlled trial.

PubMed

Mizuno, Yoshikuni; Nomoto, Masahiro; Kondo, Tomoyoshi; Hasegawa, Kazuko; Murata, Miho; Takeuchi, Masahiro; Ikeda, Junji; Tomida, Takayuki; Hattori, Nobutaka

2013-09-01

We conducted a randomized, double-blind, placebo-controlled trial to determine the safety and efficacy of transdermal rotigotine at doses up to 16 mg/24 hours in patients with early stage Parkinson's disease (PD) in Japan. Patients received once-daily rotigotine 2 to 16 mg/24 hours (mean dose, 12.8 mg/24 hours; n = 82) or placebo (n = 90) for 12 weeks. The primary endpoint was the change in Unified Parkinson's Disease Rating Scale (UPDRS) part II (activities of daily living) and part III (motor function) scores from baseline to the end of treatment. The mean (± standard deviation) changes in UPDRS part II and III scores were -8.4 ± 9.7 in the rotigotine group and -4.1 ± 8.2 in the placebo group and were significantly different (P = 0.002). More patients in the rotigotine group than in the placebo group had a ≥ 20% score reduction. No serious drug-related adverse events were reported. Rotigotine at doses up to 16 mg/24 hours was well tolerated and improved function in patients with early stage PD. © 2013 International Parkinson and Movement Disorder Society.

Differential effect of biochar upon reduction-induced mobility and bioavailability of arsenate and chromate.

PubMed

Choppala, Girish; Bolan, Nanthi; Kunhikrishnan, Anitha; Bush, Richard

2016-02-01

Heavy metals such as chromium (Cr) and arsenic (As) occur in ionic form in soil, with chromate [Cr(VI)] and arsenate As(V) being the most pre-dominant forms. The application of biochar to Cr(VI) and As(V) spiked and field contaminated soils was evaluated on the reduction processes [(Cr(VI) to Cr(III)] and [As(V) to As(III))], and subsequent mobility and bioavailability of both As(V) and Cr(VI). The assays used in this study included leaching, soil microbial activity and XPS techniques. The reduction rate of As(V) was lower than that of Cr(VI) with and without biochar addition, however, supplementation with biochar enhanced the reduction process of As(V). Leaching experiments indicated Cr(VI) was more mobile than As(V). Addition of biochar reversed the effect by reducing the mobility of Cr and increasing that of As. The presence of Cr and As in both spiked and contaminated soils reduced microbial activity, but with the addition of biochar to these soils, the microbial activity increased in the Cr(VI) contaminated soils, while it was further decreased with As(V) contaminated soils. The addition of biochar was effective in mitigating Cr toxicity by reducing Cr(VI) to Cr(III). In contrast, the conversion process of As(V) to As(III) hastened by biochar was not favourable, as As(III) is more toxic in soils. Overall, the presence of functional groups on biochar promotes reduction by providing the electrons required for reduction processes to occur as determined by XPS data. Copyright © 2015 Elsevier Ltd. All rights reserved.

Synthesis and application of Amberlite xad-4 functionalized with alizarin red-s for preconcentration and adsorption of rhodium (III)

PubMed Central

2012-01-01

A new chelating resin was prepared by coupling Amberlite XAD-4 with alizarin red-s through an azo spacer, characterized by infra-red spectroscopy and thermal analysis and studied for Rh(III) preconcentration using inductively coupled plasma atomic emission spectroscopy (ICP-AES) for rhodium monitoring in the environment. The optimum pH for sorption of the metal ion was 6.5. The sorption capacity was found 2.1 mg/g of resin for Rh(III). A recovery of 88% was obtained for the metal ion with 1.5 M HCl as eluting agent. Kinetic adsorption data were analyzed by adsorption and desorption times of Rh(III) on modified resin. Scat chard analysis revealed that the homogeneous binding sites were formed in the polymers. The linear regression equation was Q/C = –1.3169Q + 27.222 (R2 = 0.9239), for Rh were formed in the SPE sorbent,Kd and Qmax for the affinity binding sites were calculated to be 0.76 μmol/mL and 20.67 μmol/g, respectively. The equilibrium data and parameters of Rh(III) adsorption on modified resin were analyzed by Langmuir, Freundlich, Temkin and Redlich–Peterson models. The experimental adsorption isotherm was in good concordance with Langmuir and Freundlich models (R2 > 0.998) and based on the Langmuir isotherm the maximum amount of adsorption (qmax) was 4.842 mg/g. The method was applied for rhodium ions determination in environmental samples. with high recovery (>80%). PMID:23369526

LEAVING THE DARK AGES WITH AMIGA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manrique, Alberto; Salvador-Solé, Eduard; Juan, Enric

2015-01-01

We present an Analytic Model of Intergalactic-medium and GAlaxy (AMIGA) evolution since the dark ages. AMIGA is in the spirit of the popular semi-analytic models of galaxy formation, although it does not use halo merger trees but interpolates halo properties in grids that are progressively built. This strategy is less memory-demanding and allows one to start modeling at sufficiently high redshifts and low halo masses to have trivial boundary conditions. The number of free parameters is minimized by making a causal connection between physical processes usually treated as independent of each other, which leads to more reliable predictions. However, themore » strongest points of AMIGA are the following: (1) the inclusion of molecular cooling and metal-poor, population III (Pop III) stars with the most dramatic feedback and (2) accurate follow up of the temperature and volume filling factor of neutral, singly ionized, and doubly ionized regions, taking into account the distinct halo mass functions in those environments. We find the following general results. Massive Pop III stars determine the intergalactic medium metallicity and temperature, and the growth of spheroids and disks is self-regulated by that of massive black holes (MBHs) developed from the remnants of those stars. However, the properties of normal galaxies and active galactic nuclei appear to be quite insensitive to Pop III star properties due to the much higher yield of ordinary stars compared to Pop III stars and the dramatic growth of MBHs when normal galaxies begin to develop, which cause the memory loss of the initial conditions.« less

Synthesis and application of Amberlite xad-4 functionalized with alizarin red-s for preconcentration and adsorption of rhodium (III).

PubMed

Sid Kalal, Hossein; Panahi, Homayon Ahmad; Hoveidi, Hassan; Taghiof, Mohammad; Menderjani, Mahnaz Taheri

2012-09-18

A new chelating resin was prepared by coupling Amberlite XAD-4 with alizarin red-s through an azo spacer, characterized by infra-red spectroscopy and thermal analysis and studied for Rh(III) preconcentration using inductively coupled plasma atomic emission spectroscopy (ICP-AES) for rhodium monitoring in the environment. The optimum pH for sorption of the metal ion was 6.5. The sorption capacity was found 2.1 mg/g of resin for Rh(III). A recovery of 88% was obtained for the metal ion with 1.5 M HCl as eluting agent. Kinetic adsorption data were analyzed by adsorption and desorption times of Rh(III) on modified resin. Scat chard analysis revealed that the homogeneous binding sites were formed in the polymers. The linear regression equation was Q/C = -1.3169Q + 27.222 (R2 = 0.9239), for Rh were formed in the SPE sorbent,Kd and Qmax for the affinity binding sites were calculated to be 0.76 μmol/mL and 20.67 μmol/g, respectively. The equilibrium data and parameters of Rh(III) adsorption on modified resin were analyzed by Langmuir, Freundlich, Temkin and Redlich-Peterson models. The experimental adsorption isotherm was in good concordance with Langmuir and Freundlich models (R2 > 0.998) and based on the Langmuir isotherm the maximum amount of adsorption (qmax) was 4.842 mg/g. The method was applied for rhodium ions determination in environmental samples. with high recovery (>80%).

Electronic Biosensors Based on III-Nitride Semiconductors.

PubMed

Kirste, Ronny; Rohrbaugh, Nathaniel; Bryan, Isaac; Bryan, Zachary; Collazo, Ramon; Ivanisevic, Albena

2015-01-01

We review recent advances of AlGaN/GaN high-electron-mobility transistor (HEMT)-based electronic biosensors. We discuss properties and fabrication of III-nitride-based biosensors. Because of their superior biocompatibility and aqueous stability, GaN-based devices are ready to be implemented as next-generation biosensors. We review surface properties, cleaning, and passivation as well as different pathways toward functionalization, and critically analyze III-nitride-based biosensors demonstrated in the literature, including those detecting DNA, bacteria, cancer antibodies, and toxins. We also discuss the high potential of these biosensors for monitoring living cardiac, fibroblast, and nerve cells. Finally, we report on current developments of covalent chemical functionalization of III-nitride devices. Our review concludes with a short outlook on future challenges and projected implementation directions of GaN-based HEMT biosensors.

Intergenic Transcriptional Interference Is Blocked by RNA Polymerase III Transcription Factor TFIIIB in Saccharomyces cerevisiae

PubMed Central

Korde, Asawari; Rosselot, Jessica M.; Donze, David

2014-01-01

The major function of eukaryotic RNA polymerase III is to transcribe transfer RNA, 5S ribosomal RNA, and other small non-protein-coding RNA molecules. Assembly of the RNA polymerase III complex on chromosomal DNA requires the sequential binding of transcription factor complexes TFIIIC and TFIIIB. Recent evidence has suggested that in addition to producing RNA transcripts, chromatin-assembled RNA polymerase III complexes may mediate additional nuclear functions that include chromatin boundary, nucleosome phasing, and general genome organization activities. This study provides evidence of another such “extratranscriptional” activity of assembled RNA polymerase III complexes, which is the ability to block progression of intergenic RNA polymerase II transcription. We demonstrate that the RNA polymerase III complex bound to the tRNA gene upstream of the Saccharomyces cerevisiae ATG31 gene protects the ATG31 promoter against readthrough transcriptional interference from the upstream noncoding intergenic SUT467 transcription unit. This protection is predominately mediated by binding of the TFIIIB complex. When TFIIIB binding to this tRNA gene is weakened, an extended SUT467–ATG31 readthrough transcript is produced, resulting in compromised ATG31 translation. Since the ATG31 gene product is required for autophagy, strains expressing the readthrough transcript exhibit defective autophagy induction and reduced fitness under autophagy-inducing nitrogen starvation conditions. Given the recent discovery of widespread pervasive transcription in all forms of life, protection of neighboring genes from intergenic transcriptional interference may be a key extratranscriptional function of assembled RNA polymerase III complexes and possibly other DNA binding proteins. PMID:24336746

Cloud point extraction: an alternative to traditional liquid-liquid extraction for lanthanides(III) separation.

PubMed

Favre-Réguillon, Alain; Draye, Micheline; Lebuzit, Gérard; Thomas, Sylvie; Foos, Jacques; Cote, Gérard; Guy, Alain

2004-06-17

Cloud point extraction (CPE) was used to extract and separate lanthanum(III) and gadolinium(III) nitrate from an aqueous solution. The methodology used is based on the formation of lanthanide(III)-8-hydroxyquinoline (8-HQ) complexes soluble in a micellar phase of non-ionic surfactant. The lanthanide(III) complexes are then extracted into the surfactant-rich phase at a temperature above the cloud point temperature (CPT). The structure of the non-ionic surfactant, and the chelating agent-metal molar ratio are identified as factors determining the extraction efficiency and selectivity. In an aqueous solution containing equimolar concentrations of La(III) and Gd(III), extraction efficiency for Gd(III) can reach 96% with a Gd(III)/La(III) selectivity higher than 30 using Triton X-114. Under those conditions, a Gd(III) decontamination factor of 50 is obtained.

Global small RNA chaperone Hfq and regulatory small RNAs are important virulence regulators in Erwinia amylovora.

PubMed

Zeng, Quan; McNally, R Ryan; Sundin, George W

2013-04-01

Hfq is a global small RNA (sRNA) chaperone that interacts with Hfq-regulated sRNAs and functions in the posttranscriptional regulation of gene expression. In this work, we identified Hfq to be a virulence regulator in the Gram-negative fire blight pathogen Erwinia amylovora. Deletion of hfq in E. amylovora Ea1189 significantly reduced bacterial virulence in both immature pear fruits and apple shoots. Analysis of virulence determinants in strain Ea1189Δhfq showed that Hfq exerts pleiotropic regulation of amylovoran exopolysaccharide production, biofilm formation, motility, and the type III secretion system (T3SS). Further characterization of biofilm regulation by Hfq demonstrated that Hfq limits bacterial attachment to solid surfaces while promoting biofilm maturation. Characterization of T3SS regulation by Hfq revealed that Hfq positively regulates the translocation and secretion of the major type III effector DspE and negatively controls the secretion of the putative translocator HrpK and the type III effector Eop1. Lastly, 10 Hfq-regulated sRNAs were identified using a computational method, and two of these sRNAs, RprA and RyhA, were found to be required for the full virulence of E. amylovora.

Global Small RNA Chaperone Hfq and Regulatory Small RNAs Are Important Virulence Regulators in Erwinia amylovora

PubMed Central

Zeng, Quan; McNally, R. Ryan

2013-01-01

Hfq is a global small RNA (sRNA) chaperone that interacts with Hfq-regulated sRNAs and functions in the posttranscriptional regulation of gene expression. In this work, we identified Hfq to be a virulence regulator in the Gram-negative fire blight pathogen Erwinia amylovora. Deletion of hfq in E. amylovora Ea1189 significantly reduced bacterial virulence in both immature pear fruits and apple shoots. Analysis of virulence determinants in strain Ea1189Δhfq showed that Hfq exerts pleiotropic regulation of amylovoran exopolysaccharide production, biofilm formation, motility, and the type III secretion system (T3SS). Further characterization of biofilm regulation by Hfq demonstrated that Hfq limits bacterial attachment to solid surfaces while promoting biofilm maturation. Characterization of T3SS regulation by Hfq revealed that Hfq positively regulates the translocation and secretion of the major type III effector DspE and negatively controls the secretion of the putative translocator HrpK and the type III effector Eop1. Lastly, 10 Hfq-regulated sRNAs were identified using a computational method, and two of these sRNAs, RprA and RyhA, were found to be required for the full virulence of E. amylovora. PMID:23378513

LOWER EXTREMITY FUNCTIONAL TESTS AND RISK OF INJURY IN DIVISION III COLLEGIATE ATHLETES

PubMed Central

Heiderscheit, Bryan C.; Manske, Robert C.; Niemuth, Paul E.; Rauh, Mitchell J.

2013-01-01

Purpose/Background: Functional tests have been used primarily to assess an athlete's fitness or readiness to return to sport. The purpose of this prospective cohort study was to determine the ability of the standing long jump (SLJ) test, the single‐leg hop (SLH) for distance test, and the lower extremity functional test (LEFT) as preseason screening tools to identify collegiate athletes who may be at increased risk for a time‐loss sports‐related low back or lower extremity injury. Methods: A total of 193 Division III athletes from 15 university teams (110 females, age 19.1 ± 1.1 y; 83 males, age 19.5 ± 1.3 y) were tested prior to their sports seasons. Athletes performed the functional tests in the following sequence: SLJ, SLH, LEFT. The athletes were then prospectively followed during their sports season for occurrence of low back or LE injury. Results: Female athletes who completed the LEFT in $118 s were 6 times more likely (OR=6.4, 95% CI: 1.3, 31.7) to sustain a thigh or knee injury. Male athletes who completed the LEFT in #100 s were more likely to experience a time‐loss injury to the low back or LE (OR=3.2, 95% CI: 1.1, 9.5) or a foot or ankle injury (OR=6.7, 95% CI: 1.5, 29.7) than male athletes who completed the LEFT in 101 s or more. Female athletes with a greater than 10% side‐to‐side asymmetry between SLH distances had a 4‐fold increase in foot or ankle injury (cut point: >10%; OR=4.4, 95% CI: 1.2, 15.4). Male athletes with SLH distances (either leg) at least 75% of their height had at least a 3‐fold increase (OR=3.6, 95% CI: 1.2, 11.2 for the right LE; OR=3.6, 95% CI: 1.2, 11.2 for left LE) in low back or LE injury. Conclusions: The LEFT and the SLH tests appear useful in identifying Division III athletes at risk for a low back or lower extremity sports injury. Thus, these tests warrant further consideration as preparticipatory screening examination tools for sport injury in this population. Clinical Relevance: The single‐leg hop for distance and the lower extremity functional test, when administered to Division III athletes during the preseason, may help identify those at risk for a time‐loss low back or lower extremity injury. Level of Evidence: 2 PMID:23772338

Lower extremity functional tests and risk of injury in division iii collegiate athletes.

PubMed

Brumitt, Jason; Heiderscheit, Bryan C; Manske, Robert C; Niemuth, Paul E; Rauh, Mitchell J

2013-06-01

Functional tests have been used primarily to assess an athlete's fitness or readiness to return to sport. The purpose of this prospective cohort study was to determine the ability of the standing long jump (SLJ) test, the single-leg hop (SLH) for distance test, and the lower extremity functional test (LEFT) as preseason screening tools to identify collegiate athletes who may be at increased risk for a time-loss sports-related low back or lower extremity injury. A total of 193 Division III athletes from 15 university teams (110 females, age 19.1 ± 1.1 y; 83 males, age 19.5 ± 1.3 y) were tested prior to their sports seasons. Athletes performed the functional tests in the following sequence: SLJ, SLH, LEFT. The athletes were then prospectively followed during their sports season for occurrence of low back or LE injury. Female athletes who completed the LEFT in $118 s were 6 times more likely (OR=6.4, 95% CI: 1.3, 31.7) to sustain a thigh or knee injury. Male athletes who completed the LEFT in #100 s were more likely to experience a time-loss injury to the low back or LE (OR=3.2, 95% CI: 1.1, 9.5) or a foot or ankle injury (OR=6.7, 95% CI: 1.5, 29.7) than male athletes who completed the LEFT in 101 s or more. Female athletes with a greater than 10% side-to-side asymmetry between SLH distances had a 4-fold increase in foot or ankle injury (cut point: >10%; OR=4.4, 95% CI: 1.2, 15.4). Male athletes with SLH distances (either leg) at least 75% of their height had at least a 3-fold increase (OR=3.6, 95% CI: 1.2, 11.2 for the right LE; OR=3.6, 95% CI: 1.2, 11.2 for left LE) in low back or LE injury. The LEFT and the SLH tests appear useful in identifying Division III athletes at risk for a low back or lower extremity sports injury. Thus, these tests warrant further consideration as preparticipatory screening examination tools for sport injury in this population. The single-leg hop for distance and the lower extremity functional test, when administered to Division III athletes during the preseason, may help identify those at risk for a time-loss low back or lower extremity injury. 2.

A single-blinded, randomized, parallel group superiority trial investigating the effects of footwear and custom foot orthoses versus footwear alone in individuals with patellofemoral joint osteoarthritis: a phase II pilot trial protocol.

PubMed

Wyndow, Narelle; Crossley, Kay M; Vicenzino, Bill; Tucker, Kylie; Collins, Natalie J

2017-01-01

Patellofemoral joint osteoarthritis is a common condition, yet information regarding conservative management is lacking. Foot orthoses are an effective intervention for improving pain and function in younger individuals with patellofemoral pain and may be effective in those with patellofemoral osteoarthritis. This pilot study will seek to establish the feasibility of a phase III randomised controlled trial to investigate whether foot orthoses worn in prescribed motion controlled footwear are superior to prescribed motion control footwear alone in the management of patellofemoral osteoarthritis. This phase II pilot clinical trial is designed as a randomized, single-blind, parallel group, two arm, superiority trial. The trial will recruit 44 participants from Queensland and Tasmania, Australia. Volunteers aged 40 years and over must have clinical symptoms and radiographic evidence of patellofemoral osteoarthritis to be eligible for inclusion. Those eligible will be randomized to receive either foot orthoses and prescribed motion control shoes, or prescribed motion control shoes alone, to be worn for a period of 4 months. The feasibility of a phase III clinical trial will be evaluated by assessing factors such as recruitment rate, number of eligible participants, participant compliance with the study protocol, adverse events, and drop-out rate. A secondary aim of the study will be to determine completion rates and calculate effect sizes for patient reported outcome measures such as knee-related symptoms, function, quality of life, kinesiophobia, self-efficacy, general and mental health, and physical activity at 2 and 4 months. Primary outcomes will be reported descriptively while effect sizes and 95% confidence intervals will be calculated for the secondary outcome measures. Data will be analysed using an intention-to-treat principle. The results of this pilot trial will help determine the feasibility of a phase III clinical trial investigating whether foot orthoses plus motion control footwear are superior to motion control footwear alone in individuals with patellofemoral osteoarthritis. A Phase III clinical trial will help guide footwear and foot orthoses recommendations in the clinical management of this disorder. Retrospectively registered with the Australian New Zealand Clinical Trials Registry: ACTRN12615000002583. Date registered: 07/01/15.

Development of a Dispersive Liquid-Liquid Microextraction Method Combined with UV-Visible Spectrophotometry for Determination of Trace Aluminum(III) in Water, Wastewater, Food, Biological, and Pharmaceutical Samples.

PubMed

Birgani, Nasrin Taghipour; Elhami, Shahla

2017-01-01

A simple and sensitive method was proposed for the preconcentration of trace levels of Al(III) prior to its determination by spectrophotometry, based on dispersive liquid-liquid microextraction. The complexation of the Al(III) was performed by chelation with Eriochrome Cyanine R (ECR). In this method, cetyltrimethyl ammonium bromide (CTAB) as a dispersant was dissolved in chloroform as an extractant solvent, and then the solution was rapidly injected by a syringe into the samples containing Al(III), which had already been complexed by ECR at optimized pH. Various parameters were studied and optimized for a 10 mL sample volume. Under the optimum conditions, the LOD (3 times the SD of 10 replicate readings of the reagent blank) and the dynamic range of the calibration obtained were 0.2 ng mL-1 (7 nM) and 1.0-80.0 ng mL-1, respectively. The RSDs for eight replicate determinations of 10 and 60 ng mL-1 of Al(III) were 3.3 and 1.8%, respectively. This strategy was successfully applied to determine the Al concentration in water, wastewater, yogurt, apple, carrot, celery, bread, potato, urine, and Al-Mg syrup samples.

The effect of organic compounds in the oxidation kinetics of Cr(III) by H 2O 2

NASA Astrophysics Data System (ADS)

Pettine, Maurizio; Gennari, Francesca; Campanella, Luigi; Millero, Frank J.

2008-12-01

The oxidation of Cr(III) has been studied in NaCl solutions in the presence of two siderophore models, acetohydroxamic acid (Aha) and benzohydroxamic acid (Bha), the natural siderophore Desferal (DFOB) and the synthetic aminocarboxilate (ethylenedinitrilo)-tetra-acetic acid (EDTA) as a function of pH (8-9), ionic strength (0.01-2 M) and temperature (10-50 °C), at different Cr(III)-organic compound ratios. The addition of Aha and Bha caused the rates to increase at low ligand/Cr(III) ratios and decrease at high ratios. The variation of the pseudo first order rate constant ( k1) as a function of the ligand concentration has been attributed to the formation of three Cr(III)-organo species (1:1, 1:2, 1:3), which can form in the presence of monohydroxamic acids. A kinetic model has been developed that gives a value of 600 (min -1) for the pseudo first order rate constant k and values approaching zero for k and k. These kinetic results demonstrate that these monohydroxamic acids are able to bind with Cr(III) under experimental conditions that may occur in natural waters and can increase the oxidation rates of Cr(III) with H 2O 2 by a factor of 3.5 at an Aha/Cr(III) ratio of about 50-100. The monohydroxamic acids also affect the rates on aged products of Cr(III), suggesting that these ligands are able to affect the oxidation rates by releasing reactive Cr(III). DFOB and EDTA do not have a great effect on the oxidation of Cr(III) with H 2O 2. This is thought to be due to the much longer times they need to form complexes with Cr(III) compared to Aha and Bha. The rates for the formation of DFOB and EDTA complexes with Cr(III) are not competitive with the rates of the formation of aged Cr(III). After allowing Cr(III) and DFOB to react for 5 days to form the complex, reaction rates of Cr(III) with H 2O 2 appear to be lowered probably because of steric hindrance of the chelated Cr(III).

Bacterial iron transport: coordination properties of azotobactin, the highly fluorescent siderophore of Azotobacter vinelandii.

PubMed

Palanché, Tania; Blanc, Sylvie; Hennard, Christophe; Abdallah, Mohamed A; Albrecht-Gary, Anne-Marie

2004-02-09

Azotobacter vinelandii, a nitrogen-fixing soil bacterium, secretes in iron deficiency azotobactin delta, a highly fluorescent pyoverdin-like chromopeptidic hexadentate siderophore. The chromophore, derived from 2,3-diamino-6,7 dihydroxyquinoline, is bound to a peptide chain of 10 amino acids: (L)-Asp-(D)-Ser-(L)-Hse-Gly-(D)-beta-threo-HOAsp-(L)-Ser-(D)-Cit-(L)-Hse-(L)-Hse lactone-(D)-N(delta)-Acetyl, N(delta)-HOOrn. Azotobactin delta has three different iron(III) binding sites which are one hydroxamate group at the C-terminal end of the peptidic chain (N(delta)-Acetyl, N(delta)-HOOrn), one alpha-hydroxycarboxylic function in the middle of the chain (beta-threo-hydroxyaspartic acid), and one catechol group on the chromophore. The coordination properties of its iron(III) and iron(II) complexes were measured by spectrophotometry, potentiometry, and voltammetry after the determination of the acid-base functions of the uncomplexed free siderophore. Strongly negatively charged ferric species were observed at neutral p[H]'s corresponding to a predominant absolute configuration Lambda of the ferric complex in solution as deduced from CD measurements. The presence of an alpha-hydroxycarboxylic chelating group does not decrease the stability of the iron(III) complex when compared to the main trishydroxamate siderophores or to pyoverdins. The value of the redox potential of ferric azotobactin is highly consistent with a reductive step by physiological reductants for the iron release. Formation and dissociation kinetics of the azotobactin delta ferric complex point out that both ends of this long siderophore chain get coordinated to Fe(III) before the middle. The most striking result provided by fluorescence measurements is the lasting quenching of the fluorophore in the course of the protonation of the ferric azotobactin delta complex. Despite the release of the hydroxyacid and of the catechol, the fluorescence remains indeed quenched, when iron(III) is bound only to the hydroxamic acid, suggesting a folded conformation at this stage, around the metal ion, in contrast to the unfolded species observed for other siderophores such as ferrioxamine or pyoverdin PaA.

Molecular characterization and functional analysis of pteridine reductase in wild-type and antimony-resistant Leishmania lines.

PubMed

de Souza Moreira, Douglas; Ferreira, Rafael Fernandes; Murta, Silvane M F

2016-01-01

Pteridine reductase (PTR1) is an NADPH-dependent reductase that participates in the salvage of pteridines, which are essential to maintain growth of Leishmania. In this study, we performed the molecular characterization of ptr1 gene in wild-type (WTS) and SbIII-resistant (SbR) lines from Leishmania guyanensis (Lg), Leishmania amazonensis (La), Leishmania braziliensis (Lb) and Leishmania infantum (Li), evaluating the chromosomal location, mRNA levels of the ptr1 gene and PTR1 protein expression. PFGE results showed that the ptr1 gene is located in a 797 kb chromosomal band in all Leishmania lines analyzed. Interestingly, an additional chromosomal band of 1070 kb was observed only in LbSbR line. Northern blot results showed that the levels of ptr1 mRNA are increased in the LgSbR, LaSbR and LbSbR lines. Western blot assays using the polyclonal anti-LmPTR1 antibody demonstrated that PTR1 protein is more expressed in the LgSbR, LaSbR and LbSbR lines compared to their respective WTS counterparts. Nevertheless, no difference in the level of mRNA and protein was observed between the LiWTS and LiSbR lines. Functional analysis of PTR1 enzyme was performed to determine whether the overexpression of ptr1 gene in the WTS L. braziliensis and L. infantum lines would change the SbIII-resistance phenotype of transfected parasites. Western blot results showed that the expression level of PTR1 protein was increased in the transfected parasites compared to the non-transfected ones. IC50 analysis revealed that the overexpression of ptr1 gene in the WTS L. braziliensis line increased 2-fold the SbIII-resistance phenotype compared to the non-transfected counterpart. Furthermore, the overexpression of ptr1 gene in the WTS L. infantum line did not change the SbIII-resistance phenotype. These results suggest that the PTR1 enzyme may be implicated in the SbIII-resistance phenotype in L. braziliensis line. Copyright © 2015 Elsevier Inc. All rights reserved.

Bäcklund transformation of Painlevé III(D 8) τ function

NASA Astrophysics Data System (ADS)

Bershtein, M. A.; Shchechkin, A. I.

2017-03-01

We study the explicit formula (suggested by Gamayun, Iorgov and Lisovyy) for the Painlevé III(D 8) τ function in terms of Virasoro conformal blocks with a central charge of 1. The Painlevé equation has two types of bilinear forms, which we call Toda-like and Okamoto-like. We obtain these equations from the representation theory using an embedding of the direct sum of two Virasoro algebras in a certain superalgebra. These two types of bilinear forms correspond to the Neveu-Schwarz sector and the Ramond sector of this algebra. We also obtain the τ functions of the algebraic solutions of the Painlevé III(D 8) from the special representations of the Virasoro algebra of the highest weight (n  +  1/4)2.

Calculating Healthy Eating Index Scores Using Using DHQ III Data | EGRP/DCCPS/NCI/NIH

Cancer.gov

Discover how researchers using the Diet History Questionnaire III (DHQ III) to collect food and dietary supplement intakes can use the data to determine quality of a given dietary pattern, set of foods, or menu using the Healthy Eating Index.

Phylogeny and Expression Analyses Reveal Important Roles for Plant PKS III Family during the Conquest of Land by Plants and Angiosperm Diversification

PubMed Central

Xie, Lulu; Liu, Pingli; Zhu, Zhixin; Zhang, Shifan; Zhang, Shujiang; Li, Fei; Zhang, Hui; Li, Guoliang; Wei, Yunxiao; Sun, Rifei

2016-01-01

Polyketide synthases (PKSs) utilize the products of primary metabolism to synthesize a wide array of secondary metabolites in both prokaryotic and eukaryotic organisms. PKSs can be grouped into three distinct classes, types I, II, and III, based on enzyme structure, substrate specificity, and catalytic mechanisms. The type III PKS enzymes function as homodimers, and are the only class of PKS that do not require acyl carrier protein. Plant type III PKS enzymes, also known as chalcone synthase (CHS)-like enzymes, are of particular interest due to their functional diversity. In this study, we mined type III PKS gene sequences from the genomes of six aquatic algae and 25 land plants (1 bryophyte, 1 lycophyte, 2 basal angiosperms, 16 core eudicots, and 5 monocots). PKS III sequences were found relatively conserved in all embryophytes, but not exist in algae. We also examined gene expression patterns by analyzing available transcriptome data, and identified potential cis-regulatory elements in upstream sequences. Phylogenetic trees of dicots angiosperms showed that plant type III PKS proteins fall into three clades. Clade A contains CHS/STS-type enzymes coding genes with diverse transcriptional expression patterns and enzymatic functions, while clade B is further divided into subclades b1 and b2, which consist of anther-specific CHS-like enzymes. Differentiation regions, such as amino acids 196-207 between clades A and B, and predicted positive selected sites within α-helixes in late appeared branches of clade A, account for the major diversification in substrate choice and catalytic reaction. The integrity and location of conserved cis-elements containing MYB and bHLH binding sites can affect transcription levels. Potential binding sites for transcription factors such as WRKY, SPL, or AP2/EREBP may contribute to tissue- or taxon-specific differences in gene expression. Our data shows that gene duplications and functional diversification of plant type III PKS enzymes played a critical role in the ancient conquest of the land by early plants and angiosperm diversification. PMID:27625671

Dementia Screening Accuracy is Robust to Premorbid IQ Variation: Evidence from the Addenbrooke's Cognitive Examination-III and the Test of Premorbid Function.

PubMed

Stott, Joshua; Scior, Katrina; Mandy, William; Charlesworth, Georgina

2017-01-01

Scores on cognitive screening tools for dementia are associated with premorbid IQ. It has been suggested that screening scores should be adjusted accordingly. However, no study has examined whether premorbid IQ variation affects screening accuracy. To investigate whether the screening accuracy of a widely used cognitive screening tool for dementia, the Addenbrooke's cognitive examination-III (ACE-III), is improved by adjusting for premorbid IQ. 171 UK based adults (96 memory service attendees diagnosed with dementia and 75 healthy volunteers over the age of 65 without subjective memory impairments) completed the ACE-III and the Test of Premorbid Function (TOPF). The difference in screening performance between the ACE-III alone and the ACE-III adjusted for TOPF was assessed against a reference standard; the presence or absence of a diagnosis of dementia (Alzheimer's disease, vascular dementia, or others). Logistic regression and receiver operating curve analyses indicated that the ACE-III has excellent screening accuracy (93% sensitivity, 94% specificity) in distinguishing those with and without a dementia diagnosis. Although ACE-III scores were associated with TOPF scores, TOPF scores may be affected by having dementia and screening accuracy was not improved by accounting for premorbid IQ, age, or years of education. ACE-III screening accuracy is high and screening performance is robust to variation in premorbid IQ, age, and years of education. Adjustment of ACE-III cut-offs for premorbid IQ is not recommended in clinical practice. The analytic strategy used here may be useful to assess the impact of premorbid IQ on other screening tools.

Structure and Function of the Two Tandem WW Domains of the Pre-mRNA Splicing Factor FBP21 (Formin-binding Protein 21)*

PubMed Central

Huang, Xiaojuan; Beullens, Monique; Zhang, Jiahai; Zhou, Yi; Nicolaescu, Emilia; Lesage, Bart; Hu, Qi; Wu, Jihui; Bollen, Mathieu; Shi, Yunyu

2009-01-01

Human FBP21 (formin-binding protein 21) contains a matrin-type zinc finger and two tandem WW domains. It is a component of the spliceosomes and interacts with several established splicing factors. Here we demonstrate for the first time that FBP21 is an activator of pre-mRNA splicing in vivo and that its splicing activation function and interaction with the splicing factor SIPP1 (splicing factor that interacts with PQBP1 and PP1) are both mediated by the two tandem WW domains of group III. We determined the solution structure of the tandem WW domains of FBP21 and found that the WW domains recognize peptide ligands containing either group II (PPLP) or group III (PPR) motifs. The binding interfaces involve both the XP and XP2 grooves of the two WW domains. Significantly, the tandem WW domains of FBP21 are connected by a highly flexible region, enabling their simultaneous interaction with two proline-rich motifs of SIPP1. The strong interaction between SIPP1 and FBP21 can be explained by the conjugation of two low affinity interactions with the tandem WW domains. Our study provides a structural basis for understanding the molecular mechanism underlying the functional implication of FBP21 and the biological specificity of tandem WW domains. PMID:19592703

2D and 3D T2-weighted MR sequences for the assessment of neurovascular bundle changes after nerve-sparing radical retropubic prostatectomy with erectile function correlation.

PubMed

Panebianco, Valeria; Sciarra, Alessandro; Osimani, Marcello; Lisi, Danilo; Ciccariello, Mauro; Salciccia, Stefano; Gentile, Vincenzo; Di Silverio, Franco; Passariello, Roberto

2009-01-01

The aim of this study was to assess the capability of a 3D isotropic MRI T2-weighted sequence (3D T2 ISO) in the depiction of changes of neurovascular bundles (NVBs) after bilateral nerve-sparing radical retropubic prostatectomy (RRP). Furthermore, our aim was also to introduce a new MRI classification score of the NVB alteration patterns using the International Index Erectile Function Five-Item (IIEF-5) score as standard of reference. Fifty-three consecutive patients were postoperatively submitted to two MR examinations, including both 2D TSE T2-weighted (2D T2) and 3D T2 ISO sequences. Image findings were scored using a relative five-point classification and correlated with the postoperative IIEF-5 score. Radiologists attributed 13.2% of patients to class 0, 11.3% to class I, 34% to class II, 24.5% to class III, and 16.9% to class IV. With 3D T2 ISO images, the same radiologists determined 43.3% class 0, 32% class I, 11.4% class II, 7.5% class III, and 5.7% class IV. In all cases, the correlation and regression analysis between the 3D T2 ISO and IIEF-5 score resulted in higher coefficients values. The 3D sequence correlated most closely with patients' grading of erectile function.

How Do Patients and Parents Decide for Orthodontic Treatment-Effects of Malocclusion, Personal Expectations, Education and Media.

PubMed

Tuncer, C; Canigur Bavbek, N; Balos Tuncer, B; Ayhan Bani, A; Çelik, B

2015-01-01

To examine patients' and parents' perceptions and expectations from orthodontic treatment. 491 patients (274 female, 217 male) aged 14-22 years, and 399 parents (245 female, 154 male) completed a questionnaire about preferences, needs and expectations about orthodontic treatment, and scored the present problem. Continuous variables were compared by Mann-Whitney U and Kruskal-Wallis tests, whereas Chi-square test was used for categorical variables. Patients'(77.1%) and parents'(84.6%), decision about orthodontic treatments were influenced by suggestion of dentists. Patients who decided to attend to clinic by themselves were higher than parents (p=0.006). Dental aesthetics was the determinant factor for treatment demand for patients(61.0%) and parents(57.3%). Improvement in oral functions was more important for Class III patients than Class I patients (p=0.040). Adult patients/parents with higher education gave more importance to oral functions as well as dental aesthetics (p=0.031). There was no difference among Angle classifications regarding orthodontic problem scores. Parents found media sources valuable (p=0.018) but majority expected dentists for information about orthodontic treatments. Education degree of adult patients/parents effected this decision(p=0.002). Desire to have better dental aesthetics was the primary motivating factor for all participants. Clinicians should consider concerns of Class III patients about oral functions during treatment planning.

Synthesis and characterization of a porphyrazine-Gd(III) MRI contrast agent and in vivo imaging of a breast cancer xenograft model.

PubMed

Trivedi, Evan R; Ma, Zhidong; Waters, Emily A; Macrenaris, Keith W; Subramanian, Rohit; Barrett, Anthony G M; Meade, Thomas J; Hoffman, Brian M

2014-01-01

Porphyrazines (Pz), or tetraazaporphyrins, are being studied for their potential use in detection and treatment of cancer. Here, an amphiphilic Cu-Pz-Gd(III) conjugate has been prepared via azide-alkyne Huisgen cycloaddition or 'click' chemistry between an azide functionalized Pz and alkyne functionalized DOTA-Gd(III) analog for use as an MRI contrast agent. This agent, Cu-Pz-Gd(III), is synthesized in good yield and exhibits solution-phase ionic relaxivity (r1  = 11.5 mM(-1) s(-1)) that is approximately four times higher than that of a clinically used monomeric Gd(III) contrast agent, DOTA-Gd(III). Breast tumor cells (MDA-MB-231) associate with Cu-Pz-Gd(III) in vitro, where significant contrast enhancement (9.336 ± 0.335 contrast-to-noise ratio) is observed in phantom cell pellet MR images. This novel contrast agent was administered in vivo to an orthotopic breast tumor model in athymic nude mice and MR images were collected. The average T1 of tumor regions in mice treated with 50 mg kg(-1) Cu-Pz-Gd(III) decreased relative to saline-treated controls. Furthermore, the decrease in T1 was persistent relative to mice treated with the monomeric Gd(III) contrast agent. An ex vivo biodistribution study confirmed that Cu-Pz-Gd(III) accumulates in the tumors and is rapidly cleared, primarily through the kidneys. Differential accumulation and T1 enhancement by Cu-Pz-Gd(III) in the tumor's core relative to the periphery offer preliminary evidence that this agent would find application in the imaging of necrotic tissue. Copyright © 2014 John Wiley & Sons, Ltd.

Determination of the moisture content of bromobutyl rubber stoppers as a function of processing: implications for the stability of lyophilized products.

PubMed

Templeton, Allen C; Placek, Jiri; Xu, Hui; Mahajan, Rajiv; Hunke, William A; Reed, Robert A

2003-01-01

The purpose of the present study is to apply and contrast several analytical techniques to understand the change in moisture content of 20 mm diameter bromobutyl rubber stoppers as a function of typical stopper processing conditions. Three separate methods were examined and Karl-Fischer titration and techniques based on capacitance measurements at a thin-film sensor were found to provide comparable results. Stopper moisture levels were examined in stoppers: (i) as received from the manufacturer, (ii) following steam sterilization, (iii) as a function of various drying cycles, and (iv) during simulated hold conditions prior to use. Finally, the transfer of moisture from stopper to an actual product is examined on storage and general agreement observed between stopper drying conditions and cake moisture levels.

Influence of the upper joint surface and synovial lining in the outcome of chronic closed lock of the temporomandibular joint treated with arthroscopy.

PubMed

González-García, Raúl; Rodríguez-Campo, Francisco J; Monje, Florencio; Román-Romero, Leticia; Sastre-Pérez, Jesús; Usandizaga, José L Gil-Díez

2010-01-01

Temporomandibular joint (TMJ) arthroscopy has been reported to be an effective and reliable technique for the treatment of chronic closed lock (CCL) of the TMJ. The purpose of the present study was to evaluate whether the status of the joint surface and the synovial lining directly visualized with arthroscopy could determine postoperative results in patients with CCL of the TMJ. In all, 257 of 500 patients (344 joints) fulfilled the inclusion criteria for CCL of the TMJ. Of these patients, 172 with unilateral TMJ involvement were finally selected for the study. Synovitis and chondromalacia were chosen as the main features for evaluation of the joint surface and synovial lining. Two groups of patients were established: 1) patients with scarce affectation (synovitis grades I-II and chondromalacia grades I-II); and 2) patients with severe affectation (synovitis grades III-IV and/or chondromalacia grades III-IV). Pain and maximal interincisal opening were chosen as dependent variables. All patients were assessed at 1, 3, 6, 12, and 24 months postoperatively. The paired-samples Student's t test was used to compare mean values for pain (using a visual analog scale) and maximal interincisal opening (MIO) both pre- and postoperatively. The Student's t test for unpaired data was applied for the statistical analysis. A P value less than .05 was considered statistically significant. Synovitis grades I-II were arthroscopically observed in 87 (50.58%) patients, whereas synovitis grades III-IV were present in 72 (41.86%) patients. Chondromalacia grades I-II were arthroscopically observed in 66 (38.37%) patients, whereas chondromalacia grades III-IV were present in 54 (31.39%) patients. A statistically significant decrease in pain (P < .001) with a parallel increase in mouth opening (P < .001) after arthroscopy was observed for patients with synovitis I-II, synovitis III-IV, chondromalacia I-II, and chondromalacia III-IV during the whole follow-up period. A significant difference (P = .01) in relation to VAS score was observed between patients with synovitis I-II and patients with synovitis III-IV at month 6 postoperatively. However, this difference did not persist during the rest of the follow-up period, as was the case in relation to mouth opening. No significant differences were observed in relation to decrease of pain and increase of MIO between patients with chondromalacia I-II and patients with chondromalacia III-IV at any time during the follow-up period. Although mean values for pain were lower in patients with synovitis I-II plus chondromalacia I-II in comparison to patients with synovitis III-IV plus chondromalacia III-IV for the whole follow-up period, no statistical significant differences were observed. In relation to the increase in mouth opening, slightly higher values were observed for patients with synovitis I-II plus chondromalacia I-II, although no statistical differences were observed with regard to patients presenting with synovitis III-IV plus chondromalacia III-IV. A significant decrease in pain with a parallel increase in MIO was achieved from month 1 postoperatively in patients with any grade of synovitis and/or chondromalacia. No statistical difference in pain or function was observed between patients with scarce involvement of the joint surface and the synovial lining and patients with severe involvement after arthroscopy.

Atomic Structure of Interface States in Silicon Heterojunction Solar Cells

NASA Astrophysics Data System (ADS)

George, B. M.; Behrends, J.; Schnegg, A.; Schulze, T. F.; Fehr, M.; Korte, L.; Rech, B.; Lips, K.; Rohrmüller, M.; Rauls, E.; Schmidt, W. G.; Gerstmann, U.

2013-03-01

Combining orientation dependent electrically detected magnetic resonance and g tensor calculations based on density functional theory we assign microscopic structures to paramagnetic states involved in spin-dependent recombination at the interface of hydrogenated amorphous silicon crystalline silicon (a-Si:H/c-Si) heterojunction solar cells. We find that (i) the interface exhibits microscopic roughness, (ii) the electronic structure of the interface defects is mainly determined by c-Si, (iii) we identify the microscopic origin of the conduction band tail state in the a-Si:H layer, and (iv) present a detailed recombination mechanism.

Autonomous navigation - The ARMMS concept. [Autonomous Redundancy and Maintenance Management Subsystem

NASA Technical Reports Server (NTRS)

Wood, L. J.; Jones, J. B.; Mease, K. D.; Kwok, J. H.; Goltz, G. L.; Kechichian, J. A.

1984-01-01

A conceptual design is outlined for the navigation subsystem of the Autonomous Redundancy and Maintenance Management Subsystem (ARMMS). The principal function of this navigation subsystem is to maintain the spacecraft over a specified equatorial longitude to within + or - 3 deg. In addition, the navigation subsystem must detect and correct internal faults. It comprises elements for a navigation executive and for orbit determination, trajectory, maneuver planning, and maneuver command. Each of these elements is described. The navigation subsystem is to be used in the DSCS III spacecraft.

The influence of the call with a mobile phone on heart rate variability parameters in healthy volunteers.

PubMed

Andrzejak, Ryszard; Poreba, Rafal; Poreba, Malgorzata; Derkacz, Arkadiusz; Skalik, Robert; Gac, Pawel; Beck, Boguslaw; Steinmetz-Beck, Aleksandra; Pilecki, Witold

2008-08-01

It is possible that electromagnetic field (EMF) generated by mobile phones (MP) may have an influence on the autonomic nervous system (ANS) and modulates the function of circulatory system. The aim of the study was to estimate the influence of the call with a mobile phone on heart rate variability (HRV) in young healthy people. The time and frequency domain HRV analyses were performed to assess the changes in sympathovagal balance in a group of 32 healthy students with normal electrocardiogram (ECG) and echocardiogram at rest. The frequency domain variables were computed: ultra low frequency (ULF) power, very low frequency (VLF) power, low frequency (LF) power, high frequency (HF) power and LF/HF ratio was determined. ECG Holter monitoring was recorded in standardized conditions: from 08:00 to 09:00 in the morning in a sitting position, within 20 min periods: before the telephone call (period I), during the call with use of mobile phone (period II), and after the telephone call (period III). During 20 min call with a mobile phone time domain parameters such as standard deviation of all normal sinus RR intervals (SDNN [ms]--period I: 73.94+/-25.02, period II: 91.63+/-35.99, period III: 75.06+/-27.62; I-II: p<0.05, II-III: p<0.05) and standard deviation of the averaged normal sinus RR intervals for all 5-mm segments (SDANN [ms]--period I: 47.78+/-22.69, period II: 60.72+/-27.55, period III: 47.12+/-23.21; I-II: p<0.05, II-III: p<0.05) were significantly increased. As well as very low frequency (VLF [ms2]--period I: 456.62+/-214.13, period II: 566.84+/-216.99, period III: 477.43+/-203.94; I-II: p<0.05), low frequency (LF [ms(2)]--period I: 607.97+/-201.33, period II: 758.28+/-307.90, period III: 627.09+/-220.33; I-II: p<0.01, II-III: p<0.05) and high frequency (HF [ms(2)]--period I: 538.44+/-290.63, period II: 730.31+/-445.78, period III: 590.94+/-301.64; I-II: p<0.05) components were the highest and the LF/HF ratio (period I: 1.48+/-0.38, period II: 1.16+/-0.35, period III: 1.46+/-0.40; I-II: p<0.05, II-III: p<0.05) was the lowest during a call with a mobile phone. The tone of the parasympathetic system measured indirectly by analysis of heart rate variability was increased while sympathetic tone was lowered during the call with use of a mobile phone. It was shown that the call with a mobile phone may change the autonomic balance in healthy subjects. Changes in heart rate variability during the call with a mobile phone could be affected by electromagnetic field but the influence of speaking cannot be excluded.

A long-range-corrected density functional that performs well for both ground-state properties and time-dependent density functional theory excitation energies, including charge-transfer excited states.

PubMed

Rohrdanz, Mary A; Martins, Katie M; Herbert, John M

2009-02-07

We introduce a hybrid density functional that asymptotically incorporates full Hartree-Fock exchange, based on the long-range-corrected exchange-hole model of Henderson et al. [J. Chem. Phys. 128, 194105 (2008)]. The performance of this functional, for ground-state properties and for vertical excitation energies within time-dependent density functional theory, is systematically evaluated, and optimal values are determined for the range-separation parameter, omega, and for the fraction of short-range Hartree-Fock exchange. We denote the new functional as LRC-omegaPBEh, since it reduces to the standard PBEh hybrid functional (also known as PBE0 or PBE1PBE) for a certain choice of its two parameters. Upon optimization of these parameters against a set of ground- and excited-state benchmarks, the LRC-omegaPBEh functional fulfills three important requirements: (i) It outperforms the PBEh hybrid functional for ground-state atomization energies and reaction barrier heights; (ii) it yields statistical errors comparable to PBEh for valence excitation energies in both small and medium-sized molecules; and (iii) its performance for charge-transfer excitations is comparable to its performance for valence excitations. LRC-omegaPBEh, with the parameters determined herein, is the first density functional that satisfies all three criteria. Notably, short-range Hartree-Fock exchange appears to be necessary in order to obtain accurate ground-state properties and vertical excitation energies using the same value of omega.

[Cell-ELA-based determination of binding affinity of DNA aptamer against U87-EGFRvIII cell].

PubMed

Tan, Yan; Liang, Huiyu; Wu, Xidong; Gao, Yubo; Zhang, Xingmei

2013-05-01

A15, a DNA aptamer with binding specificity for U87 glioma cells stably overexpressing the epidermal growth factor receptor variant III (U87-EGFRvIII), was generated by cell systematic evolution of ligands by exponential enrichment (cell-SELEX) using a random nucleotide library. Subsequently, we established a cell enzyme-linked assay (cell-ELA) to detect the affinity of A15 compared to an EGFR antibody. We used A15 as a detection probe and cultured U87-EGFRvIII cells as targets. Our data indicate that the equilibrium dissociation constants (K(d)) for A15 were below 100 nmol/L and had similar affinity compared to an EGFR antibody for U87-EGFRvIII. We demonstrated that the cell-ELA was a useful method to determine the equilibrium dissociation constants (K(d)) of aptamers generated by cell-SELEX.

Determination of activity coefficient of lanthanum chloride in molten LiCl-KCl eutectic salt as a function of cesium chloride and lanthanum chloride concentrations using electromotive force measurements

NASA Astrophysics Data System (ADS)

Bagri, Prashant; Simpson, Michael F.

2016-12-01

The thermodynamic behavior of lanthanides in molten salt systems is of significant scientific interest for the spent fuel reprocessing of Generation IV reactors. In this study, the apparent standard reduction potential (apparent potential) and activity coefficient of LaCl3 were determined in a molten salt solution of eutectic LiCl-KCl as a function of concentration of LaCl3. The effect of adding up to 1.40 mol % CsCl was also investigated. These properties were determined by measuring the open circuit potential of the La-La(III) redox couple in a high temperature molten salt electrochemical cell. Both the apparent potential and activity coefficient exhibited a strong dependence on concentration. A low concentration (0.69 mol %) of CsCl had no significant effect on the measured properties, while a higher concentration (1.40 mol %) of CsCl caused an increase (become more positive) in the apparent potential and activity coefficient at the higher range of LaCl3 concentrations.

Extraction techniques for arsenic species in rice flour and their speciation by HPLC-ICP-MS.

PubMed

Narukawa, Tomohiro; Suzuki, Toshihiro; Inagaki, Kazumi; Hioki, Akiharu

2014-12-01

The extraction of arsenic (As) species present in rice flour samples was investigated using different extracting solvents, and the concentration of each species was determined by HPLC-ICP-MS after heat-assisted extraction. The extraction efficiencies for total arsenic species and especially for arsenite [As(III)] and arsenate [As(V)] were investigated. As(III), As(V) and dimethylarsinic acid (DMAA) were found in the samples, and the concentration of DMAA did not vary with treatment conditions. However, the concentrations of extracted total arsenic and those of As(III) and As(V) depended on the extracting solvents. When an extracting solvent was highly acidic, the concentrations of extracted total arsenic were in good agreement with the total arsenic concentration determined by ICP-MS after microwave-assisted digestion, though a part of the As(V) was reduced to As(III) during the highly acidic extraction process. Extraction under neutral conditions increased the extracted As(V), but extracted total arsenic was decreased because a part of the As(III) could not be extracted. Optimum conditions for the extraction of As(III) and As(V) from rice flour samples are discussed to allow the accurate determinations of As(III), As(V) and DMAA in the rice flour samples. Heat block extraction techniques using 0.05 mol L(-1) HClO4 and silver-containing 0.15 mol L(-1) HNO3 were also developed. Copyright © 2014 Elsevier B.V. All rights reserved.

Atomic Resolution Structure of the Oncolytic Parvovirus LuIII by Electron Microscopy and 3D Image Reconstruction

PubMed Central

Misseldine, Adam; Geilen, Lorena; Halder, Sujata; Smith, J. Kennon; Kurian, Justin; Chipman, Paul; Janssen, Mandy; Mckenna, Robert; Baker, Timothy S.; D’Abramo, Anthony; Cotmore, Susan; Tattersall, Peter; Agbandje-McKenna, Mavis

2017-01-01

LuIII, a protoparvovirus pathogenic to rodents, replicates in human mitotic cells, making it applicable for use to kill cancer cells. This virus group includes H-1 parvovirus (H-1PV) and minute virus of mice (MVM). However, LuIII displays enhanced oncolysis compared to H-1PV and MVM, a phenotype mapped to the major capsid viral protein 2 (VP2). This suggests that within LuIII VP2 are determinants for improved tumor lysis. To investigate this, the structure of the LuIII virus-like-particle was determined using single particle cryo-electron microscopy and image reconstruction to 3.17 Å resolution, and compared to the H-1PV and MVM structures. The LuIII VP2 structure, ordered from residue 37 to 587 (C-terminal), had the conserved VP topology and capsid morphology previously reported for other protoparvoviruses. This includes a core β-barrel and α-helix A, a depression at the icosahedral 2-fold and surrounding the 5-fold axes, and a single protrusion at the 3-fold axes. Comparative analysis identified surface loop differences among LuIII, H-1PV, and MVM at or close to the capsid 2- and 5-fold symmetry axes, and the shoulder of the 3-fold protrusions. The 2-fold differences cluster near the previously identified MVM sialic acid receptor binding pocket, and revealed potential determinants of protoparvovirus tumor tropism. PMID:29084163

Bristol Stool Form Scale reliability and agreement decreases when determining Rome III stool form designations

USDA-ARS?s Scientific Manuscript database

Rater reproducibility of the Bristol Stool Form Scale (BSFS), which categorizes stools into one of seven types, is unknown. We sought to determine reliability and agreement by individual stool type and when responses are categorized by Rome III clinical designation as normal or abnormal (constipatio...

Spectrophotometric determination of dopamine hydrochloride in pharmaceutical, banana, urine and serum samples by potassium ferricyanide-Fe(III).

PubMed

Guo, Li; Zhang, Yan; Li, Quanmin

2009-12-01

In the present work, we developed a simple, sensitive and inexpensive method to determine dopamine hydrochloride using potassium ferricyanide-Fe(III) by spectrophotometry. The results show that Fe(III) is deoxidized to Fe(II) by dopamine hydrochloride at pH 4.0, and then Fe(II) reacts with potassium ferricyanide to form a soluble prussian blue (KFe(III)[Fe(II)(CN)6]). The absorbance of this product was monitored over time using a spectrophotometer at an absorption maximum of 735 nm, and the amount of dopamine hydrochloride could be calculated based on the absorbance. A good linear relationship of the concentration of dopamine hydrochloride versus absorbance was observed, and a linear regression equation of A = 0.022 + 0.16921C (microg mL(-1)) was obtained. Moreover, the apparent molar absorption coefficient for the indirect determination of dopamine hydrochloride was 3.2 x 10(4) L mol(-1) cm(-1). This described method has been used to determine dopamine hydrochloride in pharmaceutical, banana, urine and serum samples with satisfactory results.

Predictors of subjective versus objective cognitive functioning in patients with stable grades II and III glioma

PubMed Central

Gehring, Karin; Taphoorn, Martin J.B.; Sitskoorn, Margriet M.; Aaronson, Neil K.

2015-01-01

Background Studies in cancer and noncancer populations demonstrate lower than expected correlations between subjective cognitive symptoms and cognitive functioning as determined by standardized neuropsychological tests. This paper systematically examines the association between subjective and objective cognitive functioning in patients with low-grade glioma and the associations of these indicators of cognitive function with clusters of sociodemographic, clinical, and self-reported physical and mental health factors. Methods Multiple regression analyses with the subjective and 2 objective indicators of cognitive functioning as dependent variables and 4 clusters of predictor variables were conducted in 169 patients with predominantly low-grade glioma. Results Correlations between the subjective and the 2 objective cognitive indicators were negligible (0.04) to low (0.24). Objective cognitive deficits were predominantly associated with sociodemographic (older age, lower education, male sex) and clinical (left hemisphere tumor) variables, while lower ratings of subjective cognitive function were more closely related to self-reported mental health symptoms (fatigue, lower mental well-being), physical (motor) dysfunction and female sex. Self-reported communication deficits were associated significantly with both subjective and objective dysfunction. Conclusions We recommend that both subjective and objective measures of cognitive functioning, together with a measure of psychological distress, be used for comprehensive neuropsychological assessments of patients with glioma to determine which areas are most affected and which specific intervention strategies are most appropriate. PMID:26034638

Class III / short line system inventory to determine 286,000 lb (129,844 kg) railcar operational status in Kansas : final report.

DOT National Transportation Integrated Search

2017-08-01

The rail industrys recent shift towards larger and heavier railcars has influenced Class III/short line railroad operation and track maintenance costs. Class III railroads earn less than $38.1 million in annual revenue and generally operate first ...

Class III / short line system inventory to determine 286,000 lb (129,844 kg) railcar operational status in Kansas : technical summary.

DOT National Transportation Integrated Search

2017-08-01

The rail industrys recent shift towards larger and heavier railcars has influenced Class III/short line railroad operation and track maintenance costs. Class III railroads earn less than $38.1 million in annual revenue and generally operate first ...

76 FR 61291 - Approval and Promulgation of Air Quality Implementation Plans; West Virginia; Ohio; Determination...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-10-04

.... Environmental Protection Agency, Region III, 1650 Arch Street, Philadelphia, Pennsylvania 19103. D. Hand..., U.S. Environmental Protection Agency, Region III, 1650 Arch Street, Philadelphia, Pennsylvania 19103..., Environmental Protection Agency, Region III, 1650 Arch Street, Philadelphia, PA 19103-2023. The telephone number...

The Bacillus subtilis ywjI (glpX) gene encodes a class II fructose-1,6-bisphosphatase, functionally equivalent to the class III Fbp enzyme.

PubMed

Jules, Matthieu; Le Chat, Ludovic; Aymerich, Stéphane; Le Coq, Dominique

2009-05-01

We present here experimental evidence that the Bacillus subtilis ywjI gene encodes a class II fructose-1,6-bisphosphatase, functionally equivalent to the fbp-encoded class III enzyme, and constitutes with the upstream gene, murAB, an operon transcribed at the same level under glycolytic or gluconeogenic conditions.

The Bacillus subtilis ywjI (glpX) Gene Encodes a Class II Fructose-1,6-Bisphosphatase, Functionally Equivalent to the Class III Fbp Enzyme▿

PubMed Central

Jules, Matthieu; Le Chat, Ludovic; Aymerich, Stéphane; Le Coq, Dominique

2009-01-01

We present here experimental evidence that the Bacillus subtilis ywjI gene encodes a class II fructose-1,6-bisphosphatase, functionally equivalent to the fbp-encoded class III enzyme, and constitutes with the upstream gene, murAB, an operon transcribed at the same level under glycolytic or gluconeogenic conditions. PMID:19270101

Sensitized terbium(III) macrocyclic-phthalimide complexes as luminescent pH switches.

PubMed

Chen, Gaoyun; Wardle, Nicholas J; Sarris, Jason; Chatterton, Nicholas P; Bligh, S W Annie

2013-10-21

Four new macrocyclic-phthalimide ligands were synthesised via the coupling of N-(3-bromopropyl)phthalimide either to cyclen (1,4,7,10-tetraazacyclododecane) itself or its carboxylate-functionalized analogues, and photophysical studies were carried out on their corresponding Tb(III) complexes in aqueous media as a function of pH. Luminescence intensities of Tb·L1a–Tb·L3a were in ‘switched off’ mode under acidic conditions (pH < 4), and were activated on progression to basic conditions as the phthalimido functions therein were hydrolysed to their corresponding phthalamates Tb·L1b–Tb·L3b. Emission of phthalamate-based macrocyclic Tb(III) complexes Tb·L1b–Tb·L3b was in ‘switched on’ mode between pH 4 and 11, exhibiting high quantum yields (Φ) and long lifetimes (τ) of the order of milliseconds at pH ~ 6. Tb(III) emissions were found to decline with increasing number of chromophores. The values of Φ and τ were 46% and 2.4 ms respectively for Tb·L1b at pH ~ 6 when activated. This is the best pH-dependent sensor based on a Tb(III) complex reported to date, benefiting from the macrocyclic architecture of the ligand.

The binding of aluminum to mugineic acid and related compounds as studied by potentiometric titration.

PubMed

Yoshimura, Etsuro; Kohdr, Hicham; Mori, Satoshi; Hider, Robert C

2011-08-01

The phytosiderophores, mugineic acid (MA) and epi-hydroxymugineic acid (HMA), together with a related compound, nicotianamine (NA), were investigated for their ability to bind Al(III). Potentiometric titration analysis demonstrated that MA and HMA bind Al(III), in contrast to NA which does not under normal physiological conditions. With MA and HMA, in addition to the Al complex (AlL), the protonated (AlLH) and deprotonated (AlLH(-1)) complexes were identified from an analysis of titration curves, where L denotes the phytosiderophore form in which all the carboxylate functions are ionized. The equilibrium formation constants of the Al(III) phytosiderophore complexes are much smaller than those of the corresponding Fe(III) complexes. The higher selectivity of phytosiderophores for Fe(III) over Al(III) facilitates Fe(III) acquisition in alkaline conditions where free Al(III) levels are higher than free Fe(III) levels.

Identification of the lipopolysaccharide modifications controlled by the Salmonella PmrA/PmrB system mediating resistance to Fe(III) and Al(III)

PubMed Central

Nishino, Kunihiko; Hsu, Fong-Fu; Turk, John; Cromie, Michael J; Wösten, Marc M S M; Groisman, Eduardo A

2006-01-01

Iron is an essential metal but can be toxic in excess. While several homeostatic mechanisms prevent oxygen-dependent killing promoted by Fe(II), little is known about how cells cope with Fe(III), which kills by oxygen-independent means. Several Gram-negative bacterial species harbour a regulatory system – termed PmrA/PmrB – that is activated by and required for resistance to Fe(III). We now report the identification of the PmrA-regulated determinants mediating resistance to Fe(III) and Al(III) in Salmonella enterica serovar Typhimurium. We establish that these determinants remodel two regions of the lipopolysaccharide, decreasing the negative charge of this major constituent of the outer membrane. Remodelling entails the covalent modification of the two phosphates in the lipid A region with phosphoethanolamine and 4-aminoarabinose, which has been previously implicated in resistance to polymyxin B, as well as dephosphorylation of the Hep(II) phosphate in the core region by the PmrG protein. A mutant lacking the PmrA-regulated Fe(III) resistance genes bound more Fe(III) than the wild-type strain and was defective for survival in soil, suggesting that these PmrA-regulated lipopolysaccharide modifications aid Salmonella's survival and spread in non-host environments. PMID:16803591

Rhodium(III)-Catalyzed Amidation of Unactivated C(sp(3) )-H Bonds.

PubMed

Wang, He; Tang, Guodong; Li, Xingwei

2015-10-26

Nitrogenation by direct functionalization of C-H bonds represents an important strategy for constructing C-N bonds. Rhodium(III)-catalyzed direct amidation of unactivated C(sp(3) )-H bonds is rare, especially under mild reaction conditions. Herein, a broad scope of C(sp(3) )-H bonds are amidated under rhodium catalysis in high efficiency using 3-substituted 1,4,2-dioxazol-5-ones as the amide source. The protocol broadens the scope of rhodium(III)-catalyzed C(sp(3) )-H activation chemistry, and is applicable to the late-stage functionalization of natural products. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rapid oxidation of geothermal arsenic(III) in streamwaters of the eastern Sierra Nevada

USGS Publications Warehouse

Wilkie, J.A.; Hering, J.G.

1998-01-01

Arsenic redox cycling was examined in source waters of the Los Angeles Aqueduct, specifically at Hot Creek, a tributary of the Owens River. Elevated arsenic concentrations in Hot Creek result from geothermal inputs. Total arsenic and As(III) concentrations were determined in the creek and in hot spring pools along its banks. Samples were processed in the field using anion-exchange columns to separate inorganic As(III) and As(V) species. Downstream of the geothermal inputs, decreasing contributions of As(III) to total arsenic concentrations indicated rapid in-stream oxidation of As(III) to As(V) with almost complete oxidation occurring within 1200 m. Based on assumed plug flow transport and a flow velocity of about 0.4 m/s, the pseudo- first-order half-life calculated for this reaction was approximately 0.3 h. Conservative transport of total dissolved arsenic was observed over the reach. Pseudo-first-order reaction rates determined for As(III) oxidation in batch studies conducted in the field with aquatic macrophytes and/or macrophyte surface matter were comparable to the in-stream oxidation rate observed along Hot Creek. In batch kinetic studies, oxidation was not observed after sterile filtration or after the addition of antibiotics, which indicates that bacteria attached to submerged macrophytes are mediating the rapid As(III) oxidation reaction.Arsenic redox cycling was examined in source waters of the Los Angeles Aqueduct, specifically at Hot Creek, a tributary of the Owens River. Elevated arsenic concentrations in Hot Creek result from geothermal inputs. Total arsenic and As(III) concentrations were determined in the creek and in hot spring pools along its banks. Samples were processed in the field using anion-exchange columns to separate inorganic As(III) and As(V) species. Downstream of the geothermal inputs, decreasing contributions of As(III) to total arsenic concentrations indicated rapid in-stream oxidation of As(III) to As(V) with almost complete oxidation occurring within 1200 m. Based on assumed plug flow transport and a flow velocity of about 0.4 m/s, the pseudo-first-order half-life calculated for this reaction was approximately 0.3 h. Conservative transport of total dissolved arsenic was observed over the reach. Pseudo-first-order reaction rates determined for As(III) oxidation in batch studies conducted in the field with aquatic macrophytes and/or macrophyte surface matter were comparable to the in-stream oxidation rate observed along Hot Creek. In batch kinetic studies, oxidation was not observed after sterile filtration or after the addition of antibiotics, which indicates that bacteria attached to submerged macrophytes are mediating the rapid As(III) oxidation reaction.

An X-ray Absorption Fine Structure study of Au adsorbed onto the non-metabolizing cells of two soil bacterial species

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Zhen; Kenney, Janice P.L.; Fein, Jeremy B.

2015-02-09

Gram-positive and Gram-negative bacterial cells can remove Au from Au(III)-chloride solutions, and the extent of removal is strongly pH dependent. In order to determine the removal mechanisms, X-ray Absorption Fine Structure (XAFS) spectroscopy experiments were conducted on non-metabolizing biomass of Bacillus subtilis and Pseudomonas putida with fixed Au(III) concentrations over a range of bacterial concentrations and pH values. X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) data on both bacterial species indicate that more than 90% of the Au atoms on the bacterial cell walls were reduced to Au(I). In contrast to what has beenmore » observed for Au(III) interaction with metabolizing bacterial cells, no Au(0) or Au-Au nearest neighbors were observed in our experimental systems. All of the removed Au was present as adsorbed bacterial surface complexes. For both species, the XAFS data suggest that although Au-chloride-hydroxide aqueous complexes dominate the speciation of Au in solution, Au on the bacterial cell wall is characterized predominantly by binding of Au atoms to sulfhydryl functional groups and amine and/or carboxyl functional groups, and the relative importance of the sulfhydryl groups increases with increasing pH and with decreasing Au loading. The XAFS data for both microorganism species suggest that adsorption is the first step in the formation of Au nanoparticles by bacteria, and the results enhance our ability to account for the behavior of Au in bacteria-bearing geologic systems.« less

An X-ray Absorption Fine Structure study of Au adsorbed onto the non-metabolizing cells of two soil bacterial species

NASA Astrophysics Data System (ADS)

Song, Zhen; Kenney, Janice P. L.; Fein, Jeremy B.; Bunker, Bruce A.

2012-06-01

Gram-positive and Gram-negative bacterial cells can remove Au from Au(III)-chloride solutions, and the extent of removal is strongly pH dependent. In order to determine the removal mechanisms, X-ray Absorption Fine Structure (XAFS) spectroscopy experiments were conducted on non-metabolizing biomass of Bacillus subtilis and Pseudomonas putida with fixed Au(III) concentrations over a range of bacterial concentrations and pH values. X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) data on both bacterial species indicate that more than 90% of the Au atoms on the bacterial cell walls were reduced to Au(I). In contrast to what has been observed for Au(III) interaction with metabolizing bacterial cells, no Au(0) or Au-Au nearest neighbors were observed in our experimental systems. All of the removed Au was present as adsorbed bacterial surface complexes. For both species, the XAFS data suggest that although Au-chloride-hydroxide aqueous complexes dominate the speciation of Au in solution, Au on the bacterial cell wall is characterized predominantly by binding of Au atoms to sulfhydryl functional groups and amine and/or carboxyl functional groups, and the relative importance of the sulfhydryl groups increases with increasing pH and with decreasing Au loading. The XAFS data for both microorganism species suggest that adsorption is the first step in the formation of Au nanoparticles by bacteria, and the results enhance our ability to account for the behavior of Au in bacteria-bearing geologic systems.

Comparative c-type cytochrome expression analysis in Shewanella oneidensis strain MR-1 and Anaeromyxobacter dehalogenans strain 2CP-C grown with soluble and insoluble oxidised metal electron acceptors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nissen, Silke; Liu, Xiaoxin; Chourey, Karuna

2012-01-01

The genomes of Shewanella oneidensis strain MR-1 and Anaeromyxobacter dehalogenans strain 2CP-C encode 40 and 69 putative c-type cytochrome genes, respectively. Deletion mutant and biochemical studies have assigned specific functions to a few c-type cytochromes involved in electron transfer to oxidised metals in Shewanella oneidensis strain MR-1. Although promising, the genetic approach is limited to gene deletions that produce a distinct phenotype, and organism for which a genetic system is available. To more comprehensively investigate and compare c-type cytochrome expression in Shewanella oneidensis strain MR-1 and Anaeromyxobacter dehalogenans strain 2CP-C, proteomic measurements were used to characterise lysates of cells grownmore » with soluble Fe(III) (as ferric citrate) and insoluble Mn(IV) (as MnO2) as electron acceptors. Strain MR-1 expressed 19 and 20, and strain 2CP-C expressed 27 and 25 c-type cytochromes when grown with Fe(III) and Mn(IV), respectively. The majority of c-type cytochromes (77% for strain MR-1 and 63% for strain 2CP-C) were expressed under both growth conditions; however, the analysis also revealed unique c-type cytochromes that were specifically expressed in cells grown with soluble Fe(III) or insoluble Mn(IV). Proteomic characterisation proved to be a promising approach for determining the c-type cytochrome complement expressed under different growth conditions, and will help elucidating the specific functions of more c-type cytochromes that are the basis for Shewanella and Anaeromyxobacter respiratory versatility.« less

Correlating Reactivity and Selectivity to Cyclopentadienyl Ligand Properties in Rh(III)-Catalyzed C-H Activation Reactions: An Experimental and Computational Study.

PubMed

Piou, Tiffany; Romanov-Michailidis, Fedor; Romanova-Michaelides, Maria; Jackson, Kelvin E; Semakul, Natthawat; Taggart, Trevor D; Newell, Brian S; Rithner, Christopher D; Paton, Robert S; Rovis, Tomislav

2017-01-25

Cp X Rh(III)-catalyzed C-H functionalization reactions are a proven method for the efficient assembly of small molecules. However, rationalization of the effects of cyclopentadienyl (Cp X ) ligand structure on reaction rate and selectivity has been viewed as a black box, and a truly systematic study is lacking. Consequently, predicting the outcomes of these reactions is challenging because subtle variations in ligand structure can cause notable changes in reaction behavior. A predictive tool is, nonetheless, of considerable value to the community as it would greatly accelerate reaction development. Designing a data set in which the steric and electronic properties of the Cp X Rh(III) catalysts were systematically varied allowed us to apply multivariate linear regression algorithms to establish correlations between these catalyst-based descriptors and the regio-, diastereoselectivity, and rate of model reactions. This, in turn, led to the development of quantitative predictive models that describe catalyst performance. Our newly described cone angles and Sterimol parameters for Cp X ligands served as highly correlative steric descriptors in the regression models. Through rational design of training and validation sets, key diastereoselectivity outliers were identified. Computations reveal the origins of the outstanding stereoinduction displayed by these outliers. The results are consistent with partial η 5 -η 3 ligand slippage that occurs in the transition state of the selectivity-determining step. In addition to the instructive value of our study, we believe that the insights gained are transposable to other group 9 transition metals and pave the way toward rational design of C-H functionalization catalysts.

Heterologous expression of the Crassostrea gigas (Pacific oyster) alternative oxidase in the yeast Saccharomyces cerevisiae.

PubMed

Robertson, Aaron; Schaltz, Kyle; Neimanis, Karina; Staples, James F; McDonald, Allison E

2016-10-01

Alternative oxidase (AOX) is a terminal oxidase within the inner mitochondrial membrane (IMM) present in many organisms where it functions in the electron transport system (ETS). AOX directly accepts electrons from ubiquinol and is therefore capable of bypassing ETS Complexes III and IV. The human genome does not contain a gene coding for AOX, so AOX expression has been suggested as a gene therapy for a range of human mitochondrial diseases caused by genetic mutations that render Complex III and/or IV dysfunctional. An effective means of screening mutations amenable to AOX treatment remains to be devised. We have generated such a tool by heterologously expressing AOX from the Pacific oyster (Crassostrea gigas) in the yeast Saccharomyces cerevisiae under the control of a galactose promoter. Our results show that this animal AOX is monomeric and is correctly targeted to yeast mitochondria. Moreover, when expressed in yeast, Pacific oyster AOX is a functional quinol oxidase, conferring cyanide-resistant growth and myxothiazol-resistant oxygen consumption to yeast cells and isolated mitochondria. This system represents a high-throughput screening tool for determining which Complex III and IV genetic mutations in yeast will be amenable to AOX gene therapy. As many human genes are orthologous to those found in yeast, our invention represents an efficient and cost-effective way to evaluate viable research avenues. In addition, this system provides the opportunity to learn more about the localization, structure, and regulation of AOXs from animals that are not easily reared or manipulated in the lab.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Kwangwook; Kang, Seokjin; Ravindran, Sooraj

Here, we report changes at the interface between Ga-rich/In-rich GaInP vertical slabs in laterally composition modulated (LCM) GaInP as a function of the V/III ratio. The photoluminescence exhibits satellite peaks, indicating that the parasitic potential between the GaInP vertical slabs disappears as the V/III ratio decreases. However, a high V/III ratio leads to an abrupt interface, increasing the parasitic potential because of the phosphorus-amount-dependent diffusion of group-III atoms during growth. These results suggest that the V/III ratio is an important parameter that must be wisely chosen in designing optoelectronic devices incorporating LCM structure.

Safe driving and executive functions in healthy middle-aged drivers.

PubMed

León-Domínguez, Umberto; Solís-Marcos, Ignacio; Barrio-Álvarez, Elena; Barroso Y Martín, Juan Manuel; León-Carrión, José

2017-01-01

The introduction of the point system driver's license in several European countries could offer a valid framework for evaluating driving skills. This is the first study to use this framework to assess the functional integrity of executive functions in middle-aged drivers with full points, partial points or no points on their driver's license (N = 270). The purpose of this study is to find differences in executive functions that could be determinants in safe driving. Cognitive tests were used to assess attention processes, processing speed, planning, cognitive flexibility, and inhibitory control. Analyses for covariance (ANCOVAS) were used for group comparisons while adjusting for education level. The Bonferroni method was used for correcting for multiple comparisons. Overall, drivers with the full points on their license showed better scores than the other two groups. In particular, significant differences were found in reaction times on Simple and Conditioned Attention tasks (both p-values < 0.001) and in number of type-III errors on the Tower of Hanoi task (p = 0.026). Differences in reaction time on attention tasks could serve as neuropsychological markers for safe driving. Further analysis should be conducted in order to determine the behavioral impact of impaired executive functioning on driving ability.

Purification of chicken carbonic anhydrase isozyme-III (CA-III) and its measurement in White Leghorn chickens.

PubMed

Nishita, Toshiho; Tomita, Yuichiro; Yorifuji, Daisuke; Orito, Kensuke; Ochiai, Hideharu; Arishima, Kazuyosi

2011-11-26

The developmental profile of chicken carbonic anhydrase-III (CA-III) blood levels has not been previously determined or reported. We isolated CA-III from chicken muscle and investigated age-related changes in the levels of CA-III in blood. CA-III was purified from chicken muscle. The levels of CA-III in plasma and erythrocytes from 278 female chickens (aged 1-93 weeks) and 68 male chickens (aged 3-59 weeks) were determined by ELISA. The mean level of CA-III in female chicken erythrocytes (1 week old) was 4.6 μg/g of Hb, and the CA-III level did not change until 16 weeks of age. The level then increased until 63 weeks of age (11.8 μg/g of Hb), decreased to 4.7 μg/g of Hb at 73 weeks of age, and increased again until 93 weeks of age (8.6 μg/g of Hb). The mean level of CA-III in erythrocytes from male chickens (3 weeks old) was 2.4 μg/g of Hb, and this level remained steady until 59 weeks of age. The mean plasma level of CA-III in 1-week-old female chickens was 60 ng/mL, and this level was increased at 3 weeks of age (141 ng/mL) and then remained steady until 80 weeks of age (122 ng/mL). The mean plasma level of CA-III in 3-week-old male chickens was 58 ng/mL, and this level remained steady until 59 weeks of age. We observed both developmental changes and sex differences in CA-III concentrations in White Leghorn (WL) chicken erythrocytes and plasma. Simple linear regression analysis showed a significant association between the erythrocyte CA-III level and egg-laying rate in WL-chickens 16-63 weeks of age (p < 0.01).

Mollebenzylanols A and B, Highly Modified and Functionalized Diterpenoids with a 9-Benzyl-8,10-dioxatricyclo[5.2.1.01,5]decane Core from Rhododendron molle.

PubMed

Zhou, Junfei; Liu, Junjun; Dang, Ting; Zhou, Haofeng; Zhang, Hanqi; Yao, Guangmin

2018-04-06

Two highly modified and functionalized diterpenoids, mollebenzylanols A (1) and B (2), and a known grayanane diterpenoid rhodojaponin III (3) were isolated from Rhododendron molle. Their structures were determined by spectroscopic data analysis, an electronic circular dichroism (ECD) exciton chirality method, ECD calculations, and X-ray diffraction analysis of the p-bromobenzoate ester of 1 (1a). Compounds 1 and 2 possess an unprecedented diterpene carbon skeleton featuring a unique 9-benzyl-8,10-dioxatricyclo[5.2.1.0 1,5 ]decane core, and their plausible biosynthetic pathways are proposed. Their PTP1B inhibitory activity and modes of action were investigated.

New anti-cancer chemicals Ertredin and its derivatives, regulate oxidative phosphorylation and glycolysis and suppress sphere formation in vitro and tumor growth in EGFRvIII-transformed cells.

PubMed

Atsumi, Sonoko; Nosaka, Chisato; Adachi, Hayamitsu; Kimura, Tomoyuki; Kobayashi, Yoshihiko; Takada, Hisashi; Watanabe, Takumi; Ohba, Shun-Ichi; Inoue, Hiroyuki; Kawada, Manabu; Shibasaki, Masakatsu; Shibuya, Masabumi

2016-07-19

EGFRvIII is a mutant form of the epidermal growth factor receptor gene (EGFR) that lacks exons 2-7. The resulting protein does not bind to ligands and is constitutively activated. The expression of EGFRvIII is likely confined to various types of cancer, particularly glioblastomas. Although an anti-EGFRvIII vaccine is of great interest, low-molecular-weight substances are needed to obtain better therapeutic efficacy. Thus, the purpose of this study is to identify low molecular weight substances that can suppress EGFRvIII-dependent transformation. We constructed a new throughput screening system and searched for substances that decreased cell survival of NIH3T3/EGFRvIII spheres under 3-dimensional (3D)-culture conditions, but retained normal NIH3T3 cell growth under 2D-culture conditions. In vivo activity was examined using a mouse transplantation model, and derivatives were chemically synthesized. Functional characterization of the candidate molecules was investigated using an EGFR kinase assay, immunoprecipitation, western blotting, microarray analysis, quantitative polymerase chain reaction analysis, and measurement of lactate and ATP synthesis. In the course of screening 30,000 substances, a reagent, "Ertredin" was found to inhibit anchorage-independent 3D growth of sphere-forming cells transfected with EGFRvIII cDNA. Ertredin also inhibited sphere formation in cells expressing wild-type EGFR in the presence of EGF. However, it did not affect anchorage-dependent 2D growth of parental NIH3T3 cells. The 3D-growth-inhibitory activity of some derivatives, including those with new structures, was similar to Ertredin. Furthermore, we demonstrated that Ertredin suppressed tumor growth in an allograft transplantation mouse model injected with EGFRvIII- or wild-type EGFR-expressing cells; a clear toxicity to host animals was not observed. Functional characterization of Ertredin in cells expressing EGFRvIII indicated that it stimulated EGFRvIII ubiquitination, suppressed both oxidative phosphorylation and glycolysis under 3D conditions, and promoted cell apoptosis. We developed a high throughput screening method based on anchorage-independent sphere formation induced by EGFRvIII-dependent transformation. In the course of screening, we identified Ertredin, which inhibited anchorage-independent 3D growth and tumor formation in nude mice. Functional analysis suggests that Ertredin suppresses both mitochondrial oxidative phosphorylation and cytosolic glycolysis in addition to promoting EGFRvIII degradation, and stimulates apoptosis in sphere-forming, EGFRvIII-overexpressing cells.

[Weight loss in overweight or obese patients and family functioning].

PubMed

Jaramillo-Sánchez, Rosalba; Espinosa-de Santillana, Irene; Espíndola-Jaramillo, Ilia Angélica

2012-01-01

to determine the association between weight loss and family functioning. a cohort of 168 persons with overweight or obesity from 20-49 years, either sex, with no comorbidity was studied at the nutrition department. A sociodemographic data was obtained and FACES III instrument to measure family functioning was applied. At the third month a new assessment of the body mass index was measured. Descriptive statistical analysis and relative risk were done. obesity presented in 50.6 %, 59.53 % of them did not lose weight. Family dysfunction was present in 56.6 % of which 50 % did not lose weight. From 43.4 % of functional families, 9.52 % did not lose weight (p = 0.001). The probability or risk of not losing weight was to belong to a dysfunctional family is 4.03 % (CI = 2.60-6.25). A significant association was found between the variables: weight loss and family functioning. Belonging to a dysfunctional family may be a risk factor for not losing weight.

[Components and assembly of RNA-induced silencing complex].

PubMed

Song, Xue-Mei; Yan, Fei; Du, Li-Xin

2006-06-01

Degradation of homologous RNA in RNA interference is carried out by functional RNA-induced silencing complex (RISC). RISC contains Dicer, Argonaute proein, siRNA and other components. Researching structures and functions of these components is primary important for understanding assembly and functional mechanism of RISC, as well as the whole RNAi pathway. Recent research works showed that Dicer, containing RNaseIII domain, is responsible for production of siRNA at the beginning of RNAi, and guarantees the stability of RISC intermediate in assembly process. As the core component of RISC, Argonaute protein functions as slicer to cleave target RNA and offers the binding site of siRNA in RISC assembly, which are depended on PIWI domain and PAZ domain separately. Although there is only one strand of siRNA that is the guider of RISC, the double stranded structural character of siRNA is determinant of RNAi. Except those, there are still other components with unknown functions in RISC. The knowledge about RISC components and assembly now, is basis of a presumed RISC assembly model.

Efficient generation of volatile cadmium species using Ti(III) and Ti(IV) and application to determination of cadmium by cold vapor generation inductively coupled plasma mass spectrometry (CVG-ICP-MS)†

PubMed Central

Arslan, Zikri; Yilmaz, Vedat; Rose, LaKeysha

2015-01-01

In this study, a highly efficient chemical vapor generation (CVG) approach is reported for determination of cadmium (Cd). Titanium (III) and titanium (IV) were investigated for the first time as catalytic additives along with thiourea, L-cysteine and potassium cyanide (KCN) for generation of volatile Cd species. Both Ti(III) and Ti(IV) provided the highest enhancement with KCN. The improvement with thiourea was marginal (ca. 2-fold), while L-cysteine enhanced signal slightly only with Ti(III) in H2SO4. Optimum CVG conditions were 4% (v/v) HCl + 0.03 M Ti(III) + 0.16 M KCN and 2% (v/v) HNO3 + 0.03 M Ti(IV) + 0.16 M KCN with a 3% (m/v) NaBH4 solution. The sensitivity was improved about 40-fold with Ti(III) and 35-fold with Ti(IV). A limit of detection (LOD) of 3.2 ng L−1 was achieved with Ti(III) by CVG-ICP-MS. The LOD with Ti(IV) was 6.4 ng L−1 which was limited by the blank signals in Ti(IV) solution. Experimental evidence indicated that Ti(III) and Ti(IV) enhanced Cd vapor generation catalytically; for best efficiency mixing prior to reaction with NaBH4 was critical. The method was highly robust against the effects of transition metal ions. No significant suppression was observed in the presence of Co(II), Cr(III), Cu(II), Fe(III), Mn(II), Ni(II) and Zn(II) up to 1.0 μg mL−1. Among the hydride forming elements, no interference was observed from As(III) and Se(IV) at 0.5 μg mL−1 level. The depressive effects from Pb(II) and Sb(III) were not significant at 0.1 μg mL−1 while those from Bi(III) and Sn(II) were marginal. The procedures were validated with determination of Cd by CVG-ICP-MS in a number certified reference materials, including Nearshore seawater (CASS-4), Bone ash (SRM 1400), Dogfish liver (DOLT-4), Mussel tissue (SRM 2976) and Domestic Sludge (SRM 2781). PMID:26251554

[Plasma citrulline concentration as a biomarker of intestinal function in short bowel syndrome and in intestinal transplant].

PubMed

Vecino López, R; Andrés Moreno, A M; Ramos Boluda, E; Martinez-Ojinaga Nodal, E; Hernanz Macías, A; Prieto Bozano, G; Lopez Santamaria, M; Tovar Larrucea, J A

2013-10-01

Citrulline is a non-essential amino acid produced solely in the enterocyte. The aim of this study was to analyse the role of serum citrulline as a biomarker of enterocyte load in children with intestinal failure due to short bowel syndrome (SBS) and its relationship to enteral adaptation. Plasma citrulline concentration was determined by chromatography (normal value>15 μmol/L) in 57 patients (age 0.5-18 years) admitted to our Intestinal Rehabilitation Unit with intestinal failure. Those who were dehydrated, with renal insufficiency, or other conditions able to modify the results were excluded. Patients were divided into 4 groups: group i: SBS totally dependent on parenteral nutrition (PN); group ii: SBS under mixed enteral-parenteral nutrition; group iii: IF weaned from PN after a rehabilitation period; group iv: small bowel transplanted patients weaned from PN and taking a normal diet. The mean ± SD plasma citrulline values were: group i (n=15): 7.1 ± 4.1; group ii (n=11): 15.8 ± 8.9; group iii (n=13): 20.6 ± 7.5; group iv (n=25): 28.8 ± 10.1. Values were significantly lower in group i in comparison with groups ii-iii-iv (P<.001), and in group ii in comparison with groups iii-iv (P<.001). A low citrulline was associated with remnant small bowel length (P<.001, r=0.85). In group iv citrulline levels decreased >50% in 3 patients who developed moderate-severe rejection, and in one patient who developed viral enteritis. 1. Plasma citrulline could be a sensitive and specific biomarker of the residual functional enterocyte load. 2. It is related to enteral feeding tolerance. 3. Its prognostic value in the process of intestinal adaptation and as a rejection marker in small bowel transplanted patients needs to be confirmed. Copyright © 2012 Asociación Española de Pediatría. Published by Elsevier Espana. All rights reserved.

Tailored Gallium(III) chelator NOPO: synthesis, characterization, bioconjugation, and application in preclinical Ga-68-PET imaging.

PubMed

Simeček, Jakub; Zemek, Ondřej; Hermann, Petr; Notni, Johannes; Wester, Hans-Jürgen

2014-11-03

The bifunctional chelator NOPO (1,4,7-triazacyclononane-1,4-bis[methylene(hydroxymethyl)phosphinic acid]-7-[methylene(2-carboxyethyl)phosphinic acid]) shows remarkably high Ga(III) complexation efficiency and comprises one carboxylic acid moiety which is not involved into metal ion coordination. An improved synthetic protocol affords NOPO with 45% overall yield. Stepwise protonation constants (log Ka), determined by potentiometry, are 11.96, 5.22, 3.77, and 1.54; the stability constant of the Ga(III) complex is log KGaL = 25.0. Within 5 min, (68)Ga(III) incorporation by NOPO is virtually quantitative at room temperature between pH 3 and 4, and at 95 °C at pH ranging from 0.5 to 7, at NOPO concentrations of 30 μM and 10 μM, respectively. During amide bond formation at the distant carboxylate using the HATU coupling reagent, an intramolecular phosphinic acid ester (phosphilactone) is formed, which is cleaved during (68)Ga complexation or in acidic media, such as trifluoroacetic acid (TFA). Phosphilactone formation can also be suppressed by complexation of Zn(2+) prior to conjugation, the resulting zinc-containing conjugates nevertheless being suitable for direct (68)Ga-labeling. In AR42J (rat pancreatic carcinoma) xenografted CD-1 nude mice, (68)Ga-labeled NOPO-NaI(3)-octreotide conjugate ((68)Ga-NOPO-NOC) showed high and fully blockable tumor uptake (13.9 ± 5% ID/g, 120 min p.i., compared to 0.9 ± 0.4% ID/g with 5 mg/kg of nonlabeled peptide). Uptake in other tissues was generally below 3% ID/g, except appearance of excretion-related activity accumulation in kidneys. NOPO-functionalized compounds tend to be more hydrophilic than the corresponding DOTA- and NODAGA-conjugates, thus promoting fast and extensive renal excretion of (68)Ga-NOPO-radiopharmaceuticals. NOPO-functionalized peptides provide suitable pharmacokinetics in vivo and meet all requirements for efficient (68)Ga-labeling even at room temperature in a kit-like manner.

Hydration effects on the barrier function of stratum corneum lipids: Raman analysis of ceramides 2, III and 5.

PubMed

Tfayli, Ali; Jamal, Dima; Vyumvuhore, Raoul; Manfait, Michel; Baillet-Guffroy, Arlette

2013-11-07

The stratum corneum is the outermost layer of the skin; its barrier function is highly dependent on the composition and the structure as well as the organization of lipids in its extracellular matrix. Ceramides, free fatty acids and cholesterol represent the major lipid classes present in this matrix. They play an important role in maintaining the normal hydration levels required for the normal physiological function. Despite the advancement in the understanding of the structure, composition and the function of the stratum corneum (SC), the concern of "dry skin" remains important in dermatology and care research. Most studies focus on the quantification of water in the skin using different techniques including Raman spectroscopy, while the studies that investigate the effect of hydration on the quality of the barrier function of the skin are limited. Raman spectroscopy provides structural, conformational and organizational information that could help elucidate the effect of hydration on the barrier function of the skin. In order to assess the effect of relative humidity on the lipid barrier function; we used Raman spectroscopy to follow-up the evolution of the conformation and the organization of three synthetic ceramides (CER) differing from each other by the nature of their polar heads (sphingosine, phytosphingosine and α hydroxyl sphingosine), CER 2, III and 5 respectively. CER III and 5 showed a more compact and ordered organization with stronger polar interactions at intermediate relative humidity values, while CER 2 showed opposite tendencies to those observed with CER III and 5.

Posterior Temporary Fixation Versus Nonoperative Treatment for Anderson-D'Alonzo Type III Odontoid Fractures: Functional Computed Tomography Evaluation of C1-C2 Rotation.

PubMed

Guo, Qunfeng; Wang, Liang; Lu, Xuhua; Guo, Xiang; Ni, Bin

2017-04-01

To evaluate differences in radiologic and functional outcomes between C1-C2 posterior temporary fixation (PTF) and cephalocervicothoracic cast fixation for type III odontoid fractures. Data from 13 patients who underwent PTF and 13 cases who underwent cephalocervicothoracic cast fixation due to fresh type III odontoid fractures were reviewed retrospectively. All patients with fracture healing underwent a functional computed tomography scan at the final follow-up to evaluate the range of motion in C1-C2 rotation. Functional outcomes were evaluated in the form of visual analog scale for neck pain, neck stiffness, patient satisfaction, and Neck Disability Index. The outcomes were compared between the 2 groups. At the final follow up, all 26 patients achieved healing of their fractures. There were no complications associated with either treatment. The left-to-right ranges of motion of C1-C2 rotation were 41.9° ± 11.9° in the PTF group and 43.5° ± 12.0° in the cephalocervicothoracic cast fixation group. There was no statistical difference between the 2 groups regarding the C1-C2 rotation angle (P > 0.05). There also were no significant differences between 2 groups in functional outcomes evaluated by visual analog scale for neck pain, neck stiffness, Neck Disability Index, and patient satisfaction (all P > 0.05). The outcomes of PTF and cephalocervicothoracic cast fixation were comparable in the treatment of type III odontoid fractures. For type III odontoid fractures that cannot be managed by nonoperative fixation or anterior screw fixation, PTF may be the treatment of choice, because it spares the motion of the C1-C2 complex. Copyright © 2016 Elsevier Inc. All rights reserved.

Development, Translation and Validation of Enhanced Asian Rome III Questionnaires for Diagnosis of Functional Bowel Diseases in Major Asian Languages: A Rome Foundation-Asian Neurogastroenterology and Motility Association Working Team Report.

PubMed

Ghoshal, Uday C; Gwee, Kok-Ann; Chen, Minhu; Gong, Xiao R; Pratap, Nitesh; Hou, Xiaohua; Syam, Ari F; Abdullah, Murdani; Bak, Young-Tae; Choi, Myung-Gyu; Gonlachanvit, Sutep; Chua, Andrew S B; Chong, Kuck-Meng; Siah, Kewin T H; Lu, Ching-Liang; Xiong, Lishou; Whitehead, William E

2015-01-01

The development-processes by regional socio-cultural adaptation of an Enhanced Asian Rome III questionnaire (EAR3Q), a cultural adaptation of the Rome III diagnostic questionnaire (R3DQ), and its translation-validation in Asian languages are presented. As English is not the first language for most Asians, translation-validation of EAR3Q is essential. Hence, we aimed to culturally adapt the R3DQ to develop EAR3Q and linguistically validate it to show that the EAR3Q is able to allocate diagnosis according to Rome III criteria. After EAR3Q was developed by Asian experts by consensus, it was translated into Chinese, Hindi-Telugu, Indonesian, Korean and Thai, following Rome Foundation guidelines; these were then validated on native subjects (healthy [n = 60], and patients with irritable bowel syndrome [n = 59], functional dyspepsia [n = 53] and functional constipation [n = 61]) diagnosed by clinicians using Rome III criteria, negative alarm features and investigations. Experts noted words for constipation, bloating, fullness and heartburn, posed difficulty. The English back-translated questionnaires demonstrated concordance with the original EAR3Q. Sensitivity and specificity of the questionnaires were high enough to diagnose respective functional gastrointestinal disorders (gold standard: clinical diagnoses) in most except Korean and Indonesian languages. Questionnaires often uncovered overlapping functional gastrointestinal disorders. Test-retest agreement (kappa) values of the translated questionnaires were high (0.700-1.000) except in Korean (0.300-0.500) and Indonesian (0.100-0.400) languages at the initial and 2-week follow-up visit. Though Chinese, Hindi and Telugu translations were performed well, Korean and Indonesian versions were not. Questionnaires often uncovered overlapping FGIDs, which were quite common.

Mutation of Rv2887, a marR-like gene, confers Mycobacterium tuberculosis resistance to an imidazopyridine-based agent.

PubMed

Winglee, Kathryn; Lun, Shichun; Pieroni, Marco; Kozikowski, Alan; Bishai, William

2015-11-01

Drug resistance is a major problem in Mycobacterium tuberculosis control, and it is critical to identify novel drug targets and new antimycobacterial compounds. We have previously identified an imidazo[1,2-a]pyridine-4-carbonitrile-based agent, MP-III-71, with strong activity against M. tuberculosis. In this study, we evaluated mechanisms of resistance to MP-III-71. We derived three independent M. tuberculosis mutants resistant to MP-III-71 and conducted whole-genome sequencing of these mutants. Loss-of-function mutations in Rv2887 were common to all three MP-III-71-resistant mutants, and we confirmed the role of Rv2887 as a gene required for MP-III-71 susceptibility using complementation. The Rv2887 protein was previously unannotated, but domain and homology analyses suggested it to be a transcriptional regulator in the MarR (multiple antibiotic resistance repressor) family, a group of proteins first identified in Escherichia coli to negatively regulate efflux pumps and other mechanisms of multidrug resistance. We found that two efflux pump inhibitors, verapamil and chlorpromazine, potentiate the action of MP-III-71 and that mutation of Rv2887 abrogates their activity. We also used transcriptome sequencing (RNA-seq) to identify genes which are differentially expressed in the presence and absence of a functional Rv2887 protein. We found that genes involved in benzoquinone and menaquinone biosynthesis were repressed by functional Rv2887. Thus, inactivating mutations of Rv2887, encoding a putative MarR-like transcriptional regulator, confer resistance to MP-III-71, an effective antimycobacterial compound that shows no cross-resistance to existing antituberculosis drugs. The mechanism of resistance of M. tuberculosis Rv2887 mutants may involve efflux pump upregulation and also drug methylation. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Mutation of Rv2887, a marR-Like Gene, Confers Mycobacterium tuberculosis Resistance to an Imidazopyridine-Based Agent

PubMed Central

Winglee, Kathryn; Lun, Shichun; Pieroni, Marco; Kozikowski, Alan

2015-01-01

Drug resistance is a major problem in Mycobacterium tuberculosis control, and it is critical to identify novel drug targets and new antimycobacterial compounds. We have previously identified an imidazo[1,2-a]pyridine-4-carbonitrile-based agent, MP-III-71, with strong activity against M. tuberculosis. In this study, we evaluated mechanisms of resistance to MP-III-71. We derived three independent M. tuberculosis mutants resistant to MP-III-71 and conducted whole-genome sequencing of these mutants. Loss-of-function mutations in Rv2887 were common to all three MP-III-71-resistant mutants, and we confirmed the role of Rv2887 as a gene required for MP-III-71 susceptibility using complementation. The Rv2887 protein was previously unannotated, but domain and homology analyses suggested it to be a transcriptional regulator in the MarR (multiple antibiotic resistance repressor) family, a group of proteins first identified in Escherichia coli to negatively regulate efflux pumps and other mechanisms of multidrug resistance. We found that two efflux pump inhibitors, verapamil and chlorpromazine, potentiate the action of MP-III-71 and that mutation of Rv2887 abrogates their activity. We also used transcriptome sequencing (RNA-seq) to identify genes which are differentially expressed in the presence and absence of a functional Rv2887 protein. We found that genes involved in benzoquinone and menaquinone biosynthesis were repressed by functional Rv2887. Thus, inactivating mutations of Rv2887, encoding a putative MarR-like transcriptional regulator, confer resistance to MP-III-71, an effective antimycobacterial compound that shows no cross-resistance to existing antituberculosis drugs. The mechanism of resistance of M. tuberculosis Rv2887 mutants may involve efflux pump upregulation and also drug methylation. PMID:26303802

A dihydropyridine receptor alpha1s loop region critical for skeletal muscle contraction is intrinsically unstructured and binds to a SPRY domain of the type 1 ryanodine receptor.

PubMed

Cui, Yanfang; Tae, Han-Shen; Norris, Nicole C; Karunasekara, Yamuna; Pouliquin, Pierre; Board, Philip G; Dulhunty, Angela F; Casarotto, Marco G

2009-03-01

The II-III loop of the dihydropyridine receptor (DHPR) alpha(1s) subunit is a modulator of the ryanodine receptor (RyR1) Ca(2+) release channel in vitro and is essential for skeletal muscle contraction in vivo. Despite its importance, the structure of this loop has not been reported. We have investigated its structure using a suite of NMR techniques which revealed that the DHPR II-III loop is an intrinsically unstructured protein (IUP) and as such belongs to a burgeoning structural class of functionally important proteins. The loop does not possess a stable tertiary fold: it is highly flexible, with a strong N-terminal helix followed by nascent helical/turn elements and unstructured segments. Its residual structure is loosely globular with the N and C termini in close proximity. The unstructured nature of the II-III loop may allow it to easily modify its interaction with RyR1 following a surface action potential and thus initiate rapid Ca(2+) release and contraction. The in vitro binding partner for the II-III was investigated. The II-III loop interacts with the second of three structurally distinct SPRY domains in RyR1, whose function is unknown. This interaction occurs through two preformed N-terminal alpha-helical regions and a C-terminal hydrophobic element. The A peptide corresponding to the helical N-terminal region is a common probe of RyR function and binds to the same SPRY domain as the full II-III loop. Thus the second SPRY domain is an in vitro binding site for the II-III loop. The possible in vivo role of this region is discussed.

A gas-phase chemiluminescence-based analyzer for waterborne arsenic

USGS Publications Warehouse

Idowu, A.D.; Dasgupta, P.K.; Genfa, Z.; Toda, K.; Garbarino, J.R.

2006-01-01

We show a practical sequential injection/zone fluidics-based analyzer that measures waterborne arsenic. The approach is capable of differentiating between inorganic As(III) and As(V). The principle is based on generating AsH 3 from the sample in a confined chamber by borohydride reduction at controlled pH, sparging the chamber to drive the AsH3 to a small reflective cell located atop a photomultiplier tube, allowing it to react with ozone generated from ambient air, and measuring the intense chemiluminescence that results. Arsine generation and removal from solution results in isolation from the sample matrix, avoiding the pitfalls encountered in some solution-based analysis techniques. The differential determination of As(III) and As(V) is based on the different pH dependence of the reducibility of these species to AsH3. At pH ???1, both As(III) and As(V) are quantitatively converted to arsine in the presence of NaBH4. At a pH of 4-5, only As(III) is converted to arsine. In the present form, the limit of detection (S/N = 3) is 0.05 ??g/L As at pH ???1 and 0.09 ??g/L As(III) at pH ???4-5 for a 3-mL sample. The analyzer is intrinsically automated and requires 4 min per determination. It is also possible to determine As(III) first at pH 4.5 and then determine the remaining As in a sequential manner; this requires 6 min. There are no significant practical interferences. A new borohydride solution formulation permits month-long reagent stability. ?? 2006 American Chemical Society.

Prevalence of Metabolic Syndrome among Malaysians using the International Diabetes Federation, National Cholesterol Education Program and Modified World Health Organization Definitions.

PubMed

Bee, Ying Tan; Haresh, Kumar Kantilal; Rajibans, Singh

2008-03-01

The World Health Organization (WHO), National Cholesterol Education Program Adults Treatment Panel III (NCEP ATP III) and International Diabetes Federation (IDF) have proposed different criteria to diagnose metabolic syndrome (MetS). However, there is no single definition to accurately diagnose MetS. The objective of this study is to estimate the prevalence of MetS using WHO, NCEP ATP III and IDF in the Malaysian community, and to determine the concordance between these definitions for MetS. 109 men and women aged > 30 years participated in the study, and the prevalence of MetS was determined according to the three definitions. Weight, height, body mass index (BMI), waist-hip circumference, blood pressure, blood lipid profile and plasma fasting glucose were measured. In order to determine the concordance between IDF and the other two definitions, the kappa index (κ-test) was used. The prevalence of MetS (95% confidence interval) was 22.9% (22.8-23.1) by IDF definition, 16.5% (16.3-16.9) by NCEP ATP III definition and 6.4% (6.2-6.6) by modified WHO definition. The sensitivity and specificity of IDF against NCEP ATP III were 88.9% and 90.1% respectively, IDF against WHO definition were 85.7% and 81.4%. The κ statistics for the agreement of the IDF definition was 68.3 ± 0.1 with the NCEP ATP III, and 30.5 ± 0.1 with the modified WHO definition. The prevalence of the MetS among respondents using the IDF definition was highest, followed by NCEP ATP III, and finally modified WHO definition. There was a good concordance between the IDF and NCEP ATP III definitions, and a low concordance between IDF and modified WHO definitions.

Human DNA ligase III recognizes DNA ends by dynamic switching between two DNA-bound states.

PubMed

Cotner-Gohara, Elizabeth; Kim, In-Kwon; Hammel, Michal; Tainer, John A; Tomkinson, Alan E; Ellenberger, Tom

2010-07-27

Human DNA ligase III has essential functions in nuclear and mitochondrial DNA replication and repair and contains a PARP-like zinc finger (ZnF) that increases the extent of DNA nick joining and intermolecular DNA ligation, yet the bases for ligase III specificity and structural variation among human ligases are not understood. Here combined crystal structure and small-angle X-ray scattering results reveal dynamic switching between two nick-binding components of ligase III: the ZnF-DNA binding domain (DBD) forms a crescent-shaped surface used for DNA end recognition which switches to a ring formed by the nucleotidyl transferase (NTase) and OB-fold (OBD) domains for catalysis. Structural and mutational analyses indicate that high flexibility and distinct DNA binding domain features in ligase III assist both nick sensing and the transition from nick sensing by the ZnF to nick joining by the catalytic core. The collective results support a "jackknife model" in which the ZnF loads ligase III onto nicked DNA and conformational changes deliver DNA into the active site. This work has implications for the biological specificity of DNA ligases and functions of PARP-like zinc fingers.

Development of a highly sensitive and selective method for extractive spectrophotometric determination of aluminum(III) from environmental matrices, synthetic mixtures, and alloys using orthohydroxypropiophenoneisonicotinoylhydrazone.

PubMed

Ramachandraiah, C; Rajesh Kumar, J; Adinarayana Reddy, S; Lee, Jin-Young; Varada Reddy, A

2010-01-01

Orthohydroxypropiophenoneisonicotinoylhydrazone (OHPINH) is proposed as a new sensitive reagent for the spectrophotometric determination of aluminum(III). OHPINH formed a greenish-yellow colored complex with aluminum(III) in buffer solutions of pH 1 to 3. The color in pH 2 was stable for more than 48 h. The complex solution has given maximum absorbance at 390 nm when the reagent was chosen as blank and the absorbance of the reagent at this wavelength is negligible; the molar absorptivity and Sandell's sensitivity being 0.6371x10(4) L mol(-1) cm(-1) and 4.234x10(-3) microg cm(-2), respectively. The system obeys Beer's law in the range of 0.5-3.5 microg mL(-1) with excellent linearity in terms of the correlation coefficient value of 0.999. Most of the common metal ions generally found associated with aluminum(III) do not interfere. The repeatability of the method was checked by finding the relative standard deviation. The developed method has been successfully employed for the determination of aluminum(III) environmental matrices like medicinal and leafy samples, alloys, and synthetic mixtures.

On the Structural Basis for Size-selective Permeation of Organic Cations through the Voltage-gated Sodium Channel

PubMed Central

Sun, Ye-Ming; Favre, Isabelle; Schild, Laurent; Moczydlowski, Edward

1997-01-01

Recent evidence indicates that ionic selectivity in voltage-gated Na+ channels is mediated by a small number of residues in P-region segments that link transmembrane elements S5 and S6 in each of four homologous domains denoted I, II, III, and IV. Important determinants for this function appear to be a set of conserved charged residues in the first three homologous domains, Asp(I), Glu(II), and Lys(III), located in a region of the pore called the DEKA locus. In this study, we examined several Ala-substitution mutations of these residues for alterations in ionic selectivity, inhibition of macroscopic current by external Ca2+ and H+, and molecular sieving behavior using a series of organic cations ranging in size from ammonium to tetraethylammonium. Whole-cell recording of wild-type and mutant channels of the rat muscle μ1 Na+ channel stably expressed in HEK293 cells was used to compare macroscopic current–voltage behavior in the presence of various external cations and an intracellular reference solution containing Cs+ and very low Ca2+. In particular, we tested the hypothesis that the Lys residue in domain III of the DEKA locus is responsible for restricting the permeation of large organic cations. Mutation of Lys(III) to Ala largely eliminated selectivity among the group IA monovalent alkali cations (Li+, Na+, K+, Rb+, Cs+) and permitted inward current of group IIA divalent cations (Mg2+, Ca2+, Sr2+, Ba2+). This same mutation also resulted in the acquisition of permeability to many large organic cations such as methylammonium, tetramethylammonium, and tetraethylammonium, all of which are impermeant in the native channel. The results lead to the conclusion that charged residues of the DEKA locus play an important role in molecular sieving behavior of the Na+ channel pore, a function that has been previously attributed to a hypothetical region of the channel called the “selectivity filter.” A detailed examination of individual contributions of the Asp(I), Glu(II), and Lys(III) residues and the dependence on molecular size suggests that relative permeability of organic cations is a complex function of the size, charge, and polarity of these residues and cation substrates. As judged by effects on macroscopic conductance, charged residues of the DEKA locus also appear to play a role in the mechanisms of block by external Ca2+ and H+, but are not essential for the positive shift in activation voltage that is produced by these ions. PMID:9382897

Development and face validity of a cerebral visual impairment motor questionnaire for children with cerebral palsy.

PubMed

Salavati, M; Waninge, A; Rameckers, E A A; van der Steen, J; Krijnen, W P; van der Schans, C P; Steenbergen, B

2017-01-01

The objectives of this study were (i) to develop two cerebral visual impairment motor questionnaires (CVI-MQ's) for children with cerebral palsy (CP): one for children with Gross Motor Function Classification System (GMFCS) levels I, II and III and one for children with GMFCS levels IV and V; (ii) to describe their face validity and usability; and (iii) to determine their sensitivity and specificity. The initial versions of the two CVI-MQ's were developed based on literature. Subsequently, the Delphi method was used in two groups of experts, one familiar with CVI and one not familiar with CVI, in order to gain consensus about face validity and usability. The sensitivity and specificity of the CVI-MQ's were subsequently assessed in 82 children with CP with (n = 39) and without CVI (n = 43). With the receiver operating curve the cut-off scores were determined to detect possible presence or absence of CVI in children with CP. Both questionnaires showed very good face validity (percentage agreement above 96%) and good usability (percentage agreement 95%) for practical use. The CVI-MQ version for GMFCS levels I, II and III had a sensitivity of 1.00 and specificity of 0.96, with a cut-off score of 12 points or higher, and the version for GMFCS levels IV and V had a sensitivity of 0.97 and a specificity of 0.98, with a cut-off score of eight points or higher. The CVI-MQ is able to identify at-risk children with CP for the probability of having CVI. © 2016 John Wiley & Sons Ltd.

DETERMINATION OF URINARY TRIVALENT ARSENICALS (MMASIII AND DMASIII) IN INDIVIDUALS CHRONICALLY EXPOSED TO ARSENIC

EPA Science Inventory

DETERMINATION OF URINARY TRIVALENT ARSENICALS (MMAsIII and DMAsIII) IN INDIVIDUALS CHRONICALLY EXPOSED TO ARSENIC.
L. M. Del Razo1, M. Styblo2, W. R. Cullen3, and D.J. Thomas4.
1Toxicology Section, Cinvestav-IPN, Mexico, D.F., 2Univ. North Carolina, Chapel Hill, NC; 3Uni...

Comparison of spectrofluorometric and HPLC methods for the characterization of fecal porphyrins in river otters.

PubMed

Taylor, C; Duffy, L K; Plumley, F G; Bowyer, R T

2000-09-01

A spectrofluorometric method (B. Grandchamp et al., 1980, Biochem. Biophys. Acta 629, 577-586) developed for the determination of amounts of uroporphyrin I (Uro I), coproporphyrin III (Copro III), and protoporphyrin IX (Proto IX) in skin fibroblasts was compared with a high-performance liquid chromatography (HPLC) method for the analysis of porphyrins in fecal samples of river otters (Lutra canadensis). Heptacarboxylate porphyrin I and coproporphyrin I, two porphyrins determined to be critical in defining the porphyrin profile in fecal samples of river otters with the HPLC method, contributed substantially to the calculation of the concentrations of Uro I and Copro III, respectively, in standard solutions of porphyrins with the spectrofluorometric method. Fluorescent components of the fecal matrix complicated the determination of the concentrations of Uro I, Copro III, and Proto IX with the spectrofluorometric method and resulted in erroneous values for the concentrations of these porphyrins compared with values determined with the HPLC method. These results indicate that the complexity of the sample, particularly with regard to the potential presence of interfering fluorescent compounds, as well as porphyrins additional to Uro I, Copro III, and Proto IX, should be considered prior to the application of the spectrofluorometric method. An alternative HPLC method developed for the rapid characterization of porphyrin profiles in fecal samples of river otters is described. Copyright 2000 Academic Press.

Comparison of the influence of polyaspartic acid and polylysine functional groups on the adsorption at the Cr2O3-Aqueous polymer solution interface

NASA Astrophysics Data System (ADS)

Ostolska, Iwona; Wiśniewska, Małgorzata

2014-08-01

Polyamino acids are a group of synthesized polymers obtained by polymerization of a given kind of amino acid monomer. Because of high biodegradability of this class of polymers, they can be used as flocculation or stabilization agents in the environmental aspects. Therefore determination of their influence on the stability of the aqueous suspension of metal oxides is important. An influence of different functional groups of polyamino acids, their molecular weight and concentration on the adsorption at the chromium (III) oxide (Cr2O3)-aqueous solution interface was determined. Experiments were carried out for four values of solution pH varying from 3 to 10 (3, 4, 7.6 and 10, respectively). Two polymers were used: anionic polyaspartic acid (ASP) of 6800 and 27,000 as well as polylysine (LYS) of 4900 and 33,000 molecular weights. Changes of surface charge density of colloidal Cr2O3 in the presence and in the absence of macromolecular substances were determined using potentiometric titration. In these studies the influence of the concentration and molecular weight of the ionic polymers on the pHpzc value was determined. Additionally, due to the lack of appropriate literature data, potentiometric titration of the selected polymers was performed to determine pKa values.

Chemical Properties And Toxicity of Chromium(III) Nutritional Supplements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Levina, A.; Lay, P.A.

2009-05-19

The status of Cr(III) as an essential micronutrient for humans is currently under question. No functional Cr(III)-containing biomolecules have been definitively described as yet, and accumulated experience in the use of Cr(III) nutritional supplements (such as [Cr(pic){sub 3}], where pic = 2-pyridinecarboxylato) has shown no measurable benefits for nondiabetic people. Although the use of large doses of Cr(III) supplements may lead to improvements in glucose metabolism for type 2 diabetics, there is a growing concern over the possible genotoxicity of these compounds, particularly of [Cr(pic){sub 3}]. The current perspective discusses chemical transformations of Cr(III) nutritional supplements in biological media, withmore » implications for both beneficial and toxic actions of Cr(III) complexes, which are likely to arise from the same biochemical mechanisms, dependent on concentrations of the reactive species. These species include: (1) partial hydrolysis products of Cr(III) nutritional supplements, which are capable of binding to biological macromolecules and altering their functions; and (2) highly reactive Cr(VI/V/IV) species and organic radicals, formed in reactions of Cr(III) with biological oxidants. Low concentrations of these species are likely to cause alterations in cell signaling (including enhancement of insulin signaling) through interactions with the active centers of regulatory enzymes in the cell membrane or in the cytoplasm, while higher concentrations are likely to produce genotoxic DNA lesions in the cell nucleus. These data suggest that the potential for genotoxic side-effects of Cr(III) complexes may outweigh their possible benefits as insulin enhancers, and that recommendations for their use as either nutritional supplements or antidiabetic drugs need to be reconsidered in light of these recent findings.« less

Molecular and electronic structure of octahedral o-aminophenolato and o-iminobenzosemiquinonato complexes of V(V), Cr(III), Fe(III), and Co(III). Experimental determination of oxidation levels of ligands and metal ions.

PubMed

Chun, H; Verani, C N; Chaudhuri, P; Bothe, E; Bill, E; Weyhermüller, T; Wieghardt, K

2001-08-13

The coordination chemistry of the ligands 2-anilino-4,6-di-tert-butylphenol, H[L(AP)], and N,N"'-bis[2-(4,6-di-tert-butylphenol]diethylenetriamine, H(2)[(L(AP))N(L(AP))], has been studied with the first-row transition metal ions V, Cr, Fe, and Co. The ligands are noninnocent in the sense that the aminophenolato parts, [L(AP)](-) and [L(AP)-H](2)(-), can be readily oxidized to their o-iminobenzosemiquinonato, [L(ISQ)](-), and o-iminobenzoquinone, [L(ISB)], forms. The following neutral octahedral complexes have been isolated as crystalline materials, and their crystal structures have been determined by X-ray crystallography at 100 K: [Cr(III)(L(ISQ))(3)] (1), [Fe(III)(L(ISQ))(3)] (2), [Co(III)(L(ISQ))(3)] (3), [V(V)(L(ISQ))(L(AP)-H)(2)] (4), [V(V)(L(AP)-H)(2)(L(AP))] (5), and [V(V)O[(L(AP))N(L(AP)-H)

Association between the -455T>C promoter polymorphism of the APOC3 gene and the metabolic syndrome in a multi-ethnic sample.

PubMed

Pollex, Rebecca L; Ban, Matthew R; Young, T Kue; Bjerregaard, Peter; Anand, Sonia S; Yusuf, Salim; Zinman, Bernard; Harris, Stewart B; Hanley, Anthony J G; Connelly, Philip W; Huff, Murray W; Hegele, Robert A

2007-12-20

Common polymorphisms in the promoter of the APOC3 gene have been associated with hypertriglyceridemia and may impact on phenotypic expression of the metabolic syndrome (MetS). The rs7566605 marker, located near the INSIG2 gene, has been found to be associated with obesity, making it also a potential genetic determinant for MetS. The objective of this study is to examine the APOC3 -455T>C and the INSIG2 rs7566605 polymorphisms as potential genetic determinants for MetS in a multi-ethnic sample. Subjects were genotyped for both the APOC3 -455T>C and INSIG2 rs7566605 polymorphisms, and classified for the presence or absence of MetS (NCEP ATP III and IDF definitions). The total study population included 2675 subjects (> or =18 years of age) from six different geographical ancestries. For the overall study population, the prevalence of MetS was 22.6% (NCEP ATP III definition). Carriers of > or =1 copy of APOC3 -455C were more likely to have MetS (NCEP ATP III definition) than noncarriers (carrier odds ratio 1.73, 95% CI 1.40 to 2.14, adjusting for age and study group). The basis of the association was related not only to a higher proportion of -455C carriers meeting the triglyceride and high-density lipoprotein cholesterol criteria, but also the blood pressure criteria compared with wild-type homozygotes. Plasma apo C-III concentrations were not associated with APOC3 -455T>C genotype. The INSIG2 rs7566605 polymorphism was not associated with MetS or measures of obesity. Meta-analysis of the sample of multiple geographic ancestries indicated that the functional -455T>C promoter polymorphism in APOC3 was associated with an approximately 2-fold increased risk of MetS, whereas the INSIG2 rs7566605 polymorphism was not associated with MetS.

Association between the -455T>C promoter polymorphism of the APOC3 gene and the metabolic syndrome in a multi-ethnic sample

PubMed Central

Pollex, Rebecca L; Ban, Matthew R; Young, T Kue; Bjerregaard, Peter; Anand, Sonia S; Yusuf, Salim; Zinman, Bernard; Harris, Stewart B; Hanley, Anthony JG; Connelly, Philip W; Huff, Murray W; Hegele, Robert A

2007-01-01

Background Common polymorphisms in the promoter of the APOC3 gene have been associated with hypertriglyceridemia and may impact on phenotypic expression of the metabolic syndrome (MetS). The rs7566605 marker, located near the INSIG2 gene, has been found to be associated with obesity, making it also a potential genetic determinant for MetS. The objective of this study is to examine the APOC3 -455T>C and the INSIG2 rs7566605 polymorphisms as potential genetic determinants for MetS in a multi-ethnic sample. Methods Subjects were genotyped for both the APOC3 -455T>C and INSIG2 rs7566605 polymorphisms, and classified for the presence or absence of MetS (NCEP ATP III and IDF definitions). The total study population included 2675 subjects (≥18 years of age) from six different geographical ancestries. Results For the overall study population, the prevalence of MetS was 22.6% (NCEP ATP III definition). Carriers of ≥1 copy of APOC3 -455C were more likely to have MetS (NCEP ATP III definition) than noncarriers (carrier odds ratio 1.73, 95% CI 1.40 to 2.14, adjusting for age and study group). The basis of the association was related not only to a higher proportion of -455C carriers meeting the triglyceride and high-density lipoprotein cholesterol criteria, but also the blood pressure criteria compared with wild-type homozygotes. Plasma apo C-III concentrations were not associated with APOC3 -455T>C genotype. The INSIG2 rs7566605 polymorphism was not associated with MetS or measures of obesity. Conclusion Meta-analysis of the sample of multiple geographic ancestries indicated that the functional -455T>C promoter polymorphism in APOC3 was associated with an approximately 2-fold increased risk of MetS, whereas the INSIG2 rs7566605 polymorphism was not associated with MetS. PMID:18096054

THE DISCREPANT KINEMATICS OF ORLs AND CELs IN NGC 7009 AS A FUNCTION OF IONIZATION STRUCTURE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Richer, Michael G.; Georgiev, Leonid; Torres-Peimbert, Silvia

2013-08-20

We present spatially and velocity-resolved echelle spectroscopy for NGC 7009 obtained with the UVES spectrograph at the European Southern Observatory's Very Large Telescope. Our objective is to analyze the kinematics of emission lines excited by recombination and collisions with electrons to determine whether similarities or differences could be useful in elucidating the well-known abundance discrepancy derived from them. We construct position-velocity maps for recombination, fluorescence, charge transfer, and collisionally excited lines. We find a plasma component emitting in the C II, N II, O II, and Ne II recombination lines whose kinematics are discrepant: they are incompatible with the ionizationmore » structure derived from all other evidence and the kinematics derived from all of these lines are unexpectedly very similar. We find direct evidence for a recombination contribution to [N II] {lambda}5755. Once taken into account, the electron temperatures from [N II], [O III], and [Ne III] agree at a given position and velocity. The electron densities derived from [O II] and [Ar IV] are consistent with direct imaging and the distribution of hydrogen emission. The kinematics of the C II, N II, O II, and Ne II lines does not coincide with the kinematics of the [O III] and [Ne III] forbidden emission, indicating that there is an additional plasma component to the recombination emission that arises from a different volume from that giving rise to the forbidden emission from the parent ions within NGC 7009. Thus, the chemical abundances derived from either type of line are correct only for the plasma component from which they arise. Apart from [N II] {lambda}5755, we find no anomaly with the forbidden lines usually used to determine chemical abundances in ionized nebulae, so the abundances derived from them should be reliable for the medium from which they arise.« less

Postconcussive Symptoms in OEF/OIF Veterans Presenting to a Polytrauma Clinic with a History of Traumatic Brain Injury

DTIC Science & Technology

2012-04-25

Adult Intelligence Scale-III (WAIS-III; ( Wechsler , 1997a)) Symbol Search subtest. Executive function. Executive functions encompass a complex... Wechsler adult intelligence scale-Third edition. San Antonio, TX: Psychological Corporation. Wechsler , D. (1997b). Wechsler Adult Intelligence Scale...DEPARTMENT OF MEDICAL & CLINICAL PSYCHOLOGY ’f-)f-f2- David Krantz, h. - . DEPARTMENT OF MEDICAL & CLINICAL PSYCHOLOGY Committee Member Eleanor S

Cognitive Profile of Children and Adolescents with Anorexia Nervosa

PubMed Central

Kjaersdam Telléus, Gry; Jepsen, Jens Richardt; Bentz, Mette; Christiansen, Eva; Jensen, Signe O W; Fagerlund, Birgitte; Thomsen, Per Hove

2015-01-01

Objective Few studies of cognitive functioning in children and adolescents with anorexia nervosa (AN) have been conducted. The aim of this study was to examine the neurocognitive and intelligence profile of this clinical group. Method The study was a matched case–control (N = 188), multi-centre study including children and adolescents with AN (N = 94) and healthy control participants (N = 94). Results The results suggest that Full Scale Intelligence Quotient (Wechsler Intelligence Scale for Children-III/Wechsler Adult Intelligence Scale-III) in this patient group is close to the normal population mean of 100. Individuals with AN exhibited significantly worse performance in nonverbal intelligence functions (i.e. Wechsler Intelligence Scale for Children-III/Wechsler Adult Intelligence Scale-III, Perceptual Organization Index) and in verbal memory (Test of Memory and Learning—Second Edition, Memory for Stories) and motor speed (Cambridge Neuropsychological Test Automated Battery, Simple and Choice Reaction Time) compared with healthy control participants. No significant difference in set-shifting ability (Cambridge Neuropsychological Test Automated Battery, Intra-Extra Dimensional Set Shift and Trail Making Test B) was found. Conclusions Inefficiency in nonverbal intelligence functions and in specific cognitive functions was found in this study of children and adolescents with AN. © 2014 The Authors. European Eating Disorders Review published by John Wiley & Sons, Ltd. PMID:25504443

Cognitive profile of children and adolescents with anorexia nervosa.

PubMed

Kjaersdam Telléus, Gry; Jepsen, Jens Richardt; Bentz, Mette; Christiansen, Eva; Jensen, Signe O W; Fagerlund, Birgitte; Thomsen, Per Hove

2015-01-01

Few studies of cognitive functioning in children and adolescents with anorexia nervosa (AN) have been conducted. The aim of this study was to examine the neurocognitive and intelligence profile of this clinical group. The study was a matched case-control (N = 188), multi-centre study including children and adolescents with AN (N = 94) and healthy control participants (N = 94). The results suggest that Full Scale Intelligence Quotient (Wechsler Intelligence Scale for Children-III/Wechsler Adult Intelligence Scale-III) in this patient group is close to the normal population mean of 100. Individuals with AN exhibited significantly worse performance in nonverbal intelligence functions (i.e. Wechsler Intelligence Scale for Children-III/Wechsler Adult Intelligence Scale-III, Perceptual Organization Index) and in verbal memory (Test of Memory and Learning-Second Edition, Memory for Stories) and motor speed (Cambridge Neuropsychological Test Automated Battery, Simple and Choice Reaction Time) compared with healthy control participants. No significant difference in set-shifting ability (Cambridge Neuropsychological Test Automated Battery, Intra-Extra Dimensional Set Shift and Trail Making Test B) was found. Inefficiency in nonverbal intelligence functions and in specific cognitive functions was found in this study of children and adolescents with AN. © 2014 The Authors. European Eating Disorders Review published by John Wiley & Sons, Ltd.

Prognostic value of computed tomography classification systems for intra-articular calcaneus fractures.

PubMed

Swords, Michael P; Alton, Timothy B; Holt, Sarah; Sangeorzan, Bruce J; Shank, John R; Benirschke, Stephen K

2014-10-01

There are several published computed tomography (CT) classification systems for calcaneus fractures, each validated by a different standard. The goal of this study was to measure which system would best predict clinical outcomes as measured by a widely used and validated musculoskeletal health status questionnaire. Forty-nine patients with isolated intra-articular joint depression calcaneus fractures more than 2 years after treatment were identified. All had preoperative CT studies and were treated with open reduction and plate fixation using a lateral extensile approach. Four different blinded reviewers classified injuries according to the CT classification systems of Crosby and Fitzgibbons, Eastwood, and Sanders. Functional outcomes evaluated with a Musculoskeletal Functional Assessment (MFA). The mean follow-up was 4.3 years. The mean MFA score was 15.7 (SD = 11.6), which is not significantly different from published values for midfoot injuries, hindfoot injuries, or both, 1 year after injury (mean = 22.1, SD = 18.4). The classification systems of Crosby and Fitzgibbons, Eastwood, and Sanders, the number of fragments of the posterior facet, and payer status were not significantly associated with outcome as determined by the MFA. The Sanders classification trended toward significance. Anterior process comminution and surgeon's overall impression of severity were significantly associated with functional outcome. The amount of anterior process comminution was an important determinant of functional outcome with increasing anterior process comminution significantly associated with worsened functional outcome (P = .04). In addition, the surgeon's overall impression of severity of injury was predictive of functional outcome (P = .02), as determined by MFA. Level III, comparative series. © The Author(s) 2014.

Research in Functionally Distributed Computer Systems Development. Volume III. Evaluation of Conversion to a Back-End Data Base Management System.

DTIC Science & Technology

1976-03-01

RESEARCH IN FUNCTIONALLY DISTRIBUTED COMPUTER SYSTEMS DEVEI.OPME--ETClU) MAR 76 P S FISHER, F MARYANSKI DAA629-76-6-0108 UNCLASSIFIED CS-76-08AN...RESEARCH IN FUNCTIONALLY !DISTRIBUTED COMPUTER SYSTEMS DEVELOPMENT Kansas State University Virgil Wallentine Principal Investigator Approved for public...reme; disiribution unlimited DTIC \\4JWE III ELECTi"U ~E V0AI. Ill ~1ONTAUG 2 0 1981&EV .IAIN LiSP4 F U.S. ARMY COMPUTER SYSTEMS COMMAND FT BELVOIR, VA

Trauma care at rural level III trauma centers in a state trauma system.

PubMed

Helling, Thomas S

2007-02-01

Although much has been written about the benefits of trauma center care, most experiences are urban with large numbers of patients. Little is known about the smaller, rural trauma centers and how they function both independently and as part of a larger trauma system. The state of Missouri has designated three levels of trauma care. The cornerstone of rural trauma care is the state-designated Level III trauma center. These centers are required to have the presence of a trauma team and trauma surgeon but do not require orthopedic or neurosurgical coverage. The purpose of this retrospective study was to determine how Level III trauma centers compared with Level I and Level II centers in the Missouri trauma system and, secondly, how trauma surgeon experience at these centers might shape future educational efforts to optimize rural trauma care. During a 2-year period in 2002 and 2003, the state trauma registry was queried on all trauma admissions for centers in the trauma system. Demographics and patient care outcomes were assessed by level of designation. Trauma admissions to the Level III centers were examined for acuity, severity, and type of injury. The experiences with chest, abdominal, and neurologic trauma were examined in detail. A total of 24,392 patients from 26 trauma centers were examined, including all eight Level III centers. Acuity and severity of injuries were higher at Level I and II centers. A total of 2,910 patients were seen at the 8 Level III centers. Overall deaths were significantly lower at Level III centers (Level I, 4% versus Level II, 4% versus Level III, 2%, p < 0.001). Numbers of patients dying within 24 hours were no different among levels of trauma care (Level I, 37% versus Level II, 30% versus Level III, 32%). Among Level III centers 45 (1.5%) patients were admitted in shock, and 48 (2%) had a Glasgow Coma Scale score <9. Twenty-six patients had a surgical head injury (7 epidural, 19 subdural hematomas). Twenty-eight patients (1%) needed a chest or abdominal operation. There were 15 spleen and 12 liver injuries with an Abbreviated Injury Score of 4 or 5. Level III trauma centers performed as expected in a state trauma system. Acuity and severity were less as was corresponding mortality. There were a paucity of life-threatening head, chest, and abdominal injuries, which provide a challenge to the rural trauma surgeon to maintain necessary skills in management of these critical injuries.

Prevalence of functional gastrointestinal diseases in a cohort of Sri Lankan adolescents: comparison between Rome II and Rome III criteria.

PubMed

Devanarayana, Niranga Manjuri; Adhikari, Chandralatha; Pannala, Waruni; Rajindrajith, Shaman

2011-02-01

Little is known about the prevalence of functional gastrointestinal diseases (FGDs) in adolescents, especially in developing countries. This cross-sectional survey conducted in a semi-urban school in Sri Lanka, assessed the prevalence of whole spectrum of FGDs in 427 adolescents (age 12-16 years) using a validated self-administered questionnaire. According to Rome III criteria, 123 (28.8%) adolescents had FGDs. Of them, 59 (13.8%) had abdominal-pain-related FGDs [irritable bowel syndrome (IBS) 30, functional dyspepsia 15, functional abdominal pain 13 and abdominal migraine 1]. Prevalence of functional constipation, aerophagia, adolescent rumination syndrome, cyclical vomiting syndrome and non-retentive faecal incontinence were 4.2, 6.3, 4, 0.5 and 0.2%, respectively. Only 58 (13.6%) adolescents were found to have FGDs when Rome II criteria were used. In conclusion, FGDs were present in more than one-fourth of adolescents in the study group, of which IBS was the most common. Rome III criteria were able to diagnose FGDs more comprehensively than Rome II.

Relationship of Temporal Lobe Volumes to Neuropsychological Test Performance in Healthy Children

PubMed Central

Wells, Carolyn T.; Matson, Melissa A.; Kates, Wendy R.; Hay, Trisha; Horska, Alena

2008-01-01

Ecological validity of neuropsychological assessment includes the ability of tests to predict real-world functioning and/or covary with brain structures. Studies have examined the relationship between adaptive skills and test performance, with less focus on the association between regional brain volumes and neurobehavioral function in healthy children. The present study examined the relationship between temporal lobe gray matter volumes and performance on two neuropsychological tests hypothesized to measure temporal lobe functioning (Visual Perception-VP; Peabody Picture Vocabulary Test, Third Edition-PPVT-III) in 48 healthy children ages 5-18 years. After controlling for age and gender, left and right temporal and left occipital volumes were significant predictors of VP. Left and right frontal and temporal volumes were significant predictors of PPVT-III. Temporal volume emerged as the strongest lobar correlate with both tests. These results provide convergent and discriminant validity supporting VP as a measure of the “what” system; but suggest the PPVT-III as a complex measure of receptive vocabulary, potentially involving executive function demands. PMID:18513844

Space Density of Optically Selected Type 2 Quasars

NASA Astrophysics Data System (ADS)

Reyes, Reinabelle; Zakamska, Nadia L.; Strauss, Michael A.; Green, Joshua; Krolik, Julian H.; Shen, Yue; Richards, Gordon T.; Anderson, Scott F.; Schneider, Donald P.

2008-12-01

Type 2 quasars are luminous active galactic nuclei whose central regions are obscured by large amounts of gas and dust. In this paper, we present a catalog of type 2 quasars from the Sloan Digital Sky Survey, selected based on their optical emission lines. The catalog contains 887 objects with redshifts z < 0.83; this is 6 times larger than the previous version and is by far the largest sample of type 2 quasars in the literature. We derive the [O III]5007 luminosity function (LF) for 108.3 L sun < L [O III] < 1010 L sun (corresponding to intrinsic luminosities up to M[2500 Å] ~= -28 mag or bolometric luminosities up to 4 × 1047 erg s-1). This LF provides robust lower limits to the actual space density of obscured quasars due to our selection criteria, the details of the spectroscopic target selection, and other effects. We derive the equivalent LF for the complete sample of type 1 (unobscured) quasars and determine the ratio of type 2 to type 1 quasar number densities. Our data constrain this ratio to be at least ~1.5:1 for 108.3 L sun < L [O III] < 109.5 L sun at z < 0.3, and at least ~1.2:1 for L [O III] ~ 1010 L sun at 0.3 < z < 0.83. Type 2 quasars are at least as abundant as type 1 quasars in the relatively nearby universe (z <~ 0.8) for the highest luminosities.

Use of proline mutants to help solve the NMR solution structure of type III antifreeze protein.

PubMed Central

Chao, H.; Davies, P. L.; Sykes, B. D.; Sönnichsen, F. D.

1993-01-01

To help understand the structure/function relationships in antifreeze proteins (AFP), and to define the motifs required for ice binding, a Type III AFP suitable for two-dimensional (2D) NMR studies was produced in Escherichia coli. A synthetic gene for one of the Type III AFP isoforms was assembled in a T7 polymerase-directed expression vector. The 67-amino acid-long gene product differed from the natural AFP by inclusion of an N-terminal methionine but was indistinguishable in activity. The NMR spectra of this AFP were complicated by cis-trans proline isomerization from the C-terminal sequence YPPA. Substitution of this sequence by YAA eliminated isomer signals without altering the activity or structure of the mutant AFP. This variant (rQAE m1.1) was selected for sequential assignment and the secondary structure determination using 2D 1H NMR spectroscopy. Nine beta-strands are paired to form two triple-stranded antiparallel sheets and one double-stranded antiparallel sheet. Two further proline replacements, P29A and P33A, were made to delineate the role of conserved prolines in Type III AFP. These mutants were valuable in clarifying ambiguous NMR spectral assignments amongst the remaining six prolines of rQAE m1.1. In contrast to the replacement of the C-terminal prolyl residues, the exchange of P29 and P33 caused some structural changes and significantly decreased protein solubility and antifreeze activity. PMID:8401227

Biological Differences between Hanwoo longissimus dorsi and semimembranosus Muscles in Collagen Synthesis of Fibroblasts.

PubMed

Subramaniyan, Sivakumar Allur; Hwang, Inho

2017-01-01

Variations in physical toughness between muscles and animals are a function of growth rate and extend of collagen type I and III. The current study was designed to investigate the ability of growth rate, collagen concentration, collagen synthesizing and degrading genes on two different fibroblast cells derived from Hanwoo m. longissimus dorsi (LD) and semimembranosus (SM) muscles. Fibroblast cell survival time was determined for understanding about the characteristics of proliferation rate between the two fibroblasts. We examined the collagen concentration and protein expression of collagen type I and III between the two fibroblasts. The mRNA expression of collagen synthesis and collagen degrading genes to elucidate the molecular mechanisms on toughness and tenderness through collagen production between the two fibroblast cells. From our results the growth rate, collagen content and protein expression of collagen type I and III were significantly higher in SM than LD muscle fibroblast. The mRNA expressions of collagen synthesized genes were increased whereas the collagen degrading genes were decreased in SM than LD muscle. Results from confocal microscopical investigation showed increased fluorescence of collagen type I and III appearing stronger in SM than LD muscle fibroblast. These results implied that the locomotion muscle had higher fibroblast growth rate, leads to produce more collagen, and cause tougher than positional muscle. This in vitro study mirrored that background toughness of various muscles in live animal is likely associated with fibroblast growth pattern, collagen synthesis and its gene expression.

Chromium basalts - Experimental determination of redox states and partitioning among synthetic silicate phases

NASA Technical Reports Server (NTRS)

Schreiber, H. D.; Haskin, L. A.

1976-01-01

Experiments were performed on silicate compositions in the forsterite-anorthite-silica and forsterite-anorthite-diopside systems to determine the relative amounts of Cr(II), Cr(III), and Cr(VI) over a wide range of oxygen partial pressures from 10 to the -10th to 1 atm at 1500 and 1550 C. Redox states were measured by visible absorption spectroscopy and electron paramagnetic resonance spectroscopy and titration. It was found that Cr is present almost exclusively as Cr(III) in terrestrial basaltic liquids and as a mixture of Cr(III) and Cr(II) in lunar basaltic liquids.

Missense mutation in APOC3 within the C-terminal lipid binding domain of human ApoC-III results in impaired assembly and secretion of triacylglycerol-rich very low density lipoproteins: evidence that ApoC-III plays a major role in the formation of lipid precursors within the microsomal lumen.

PubMed

Qin, Wen; Sundaram, Meenakshi; Wang, Yuwei; Zhou, Hu; Zhong, Shumei; Chang, Chia-Ching; Manhas, Sanjay; Yao, Erik F; Parks, Robin J; McFie, Pamela J; Stone, Scot J; Jiang, Zhenghui G; Wang, Congrong; Figeys, Daniel; Jia, Weiping; Yao, Zemin

2011-08-05

Hepatic assembly of triacylglycerol (TAG)-rich very low density lipoproteins (VLDL) is achieved through recruitment of bulk TAG (presumably in the form of lipid droplets within the microsomal lumen) into VLDL precursor containing apolipoprotein (apo) B-100. We determined protein/lipid components of lumenal lipid droplets (LLD) in cells expressing recombinant human apoC-III (C3wt) or a mutant form (K58E, C3KE) initially identified in humans that displayed hypotriglyceridemia. Although expression of C3wt markedly stimulated secretion of TAG and apoB-100 as VLDL(1), the K58E mutation (located at the C-terminal lipid binding domain) abolished the effect in transfected McA-RH7777 cells and in apoc3-null mice. Metabolic labeling studies revealed that accumulation of TAG in LLD was decreased (by 50%) in cells expressing C3KE. A Fat Western lipid protein overlay assay showed drastically reduced lipid binding of the mutant protein. Substituting Lys(58) with Arg demonstrated that the positive charge at position 58 is crucial for apoC-III binding to lipid and for promoting TAG secretion. On the other hand, substituting both Lys(58) and Lys(60) with Glu resulted in almost entire elimination of lipid binding and loss of function in promoting TAG secretion. Thus, the lipid binding domain of apoC-III plays a key role in the formation of LLD for hepatic VLDL assembly and secretion.

Escherichia coli type III secretion system 2: a new kind of T3SS?

PubMed

Zhou, Mingxu; Guo, Zhiyan; Duan, Qiangde; Hardwidge, Philip R; Zhu, Guoqiang

2014-03-19

Type III secretion systems (T3SSs) are employed by Gram-negative bacteria to deliver effector proteins into the cytoplasm of infected host cells. Enteropathogenic Escherichia coli use a T3SS to deliver effector proteins that result in the creation of the attaching and effacing lesions. The genome sequence of the Escherichia coli pathotype O157:H7 revealed the existence of a gene cluster encoding components of a second type III secretion system, the E. coli type III secretion system 2 (ETT2). Researchers have revealed that, although ETT2 may not be a functional secretion system in most (or all) strains, it still plays an important role in bacterial virulence. This article summarizes current knowledge regarding the E. coli ETT2, including its genetic characteristics, prevalence, function, association with virulence, and prospects for future work.

The relative hydrolytic reactivities of pyrophosphites and pyrophosphates.

PubMed

Mistry, Dharmit; Powles, Nicholas

2013-09-14

The pH-rate profiles for the hydrolysis of pyrophosphate (PP(V)) and pyrophosphite (PP(III), pyro-di-H-phosphonate) are a complex function of pH, reflecting the different ionic species and their relative reactivities. PP(III) is more reactive than PP(V) at all pHs and only PP(III) shows a hydroxide-ion reaction at high pH, so it is 10(10)-fold more reactive than PP(V) in 0.1 M NaOH. The pK(a2) of PP(III) ~0.44, so the dominant species at pH's > 1 is the di-anion PP(III)(2-). Although there is no observable (NMR or ITC) binding of Mg(2+) to the PP(III) di-anion there is a modest increase in the rate of hydrolysis of PP(III) by Mg(2+). PP(III) is neither a substrate nor an inhibitor of pyrophosphatase, the enzyme that efficiently catalyses the hydrolysis of PP(V).

Arsenic removal by perilla leaf biochar in aqueous solutions and groundwater: An integrated spectroscopic and microscopic examination.

PubMed

Niazi, Nabeel Khan; Bibi, Irshad; Shahid, Muhammad; Ok, Yong Sik; Burton, Edward D; Wang, Hailong; Shaheen, Sabry M; Rinklebe, Jörg; Lüttge, Andreas

2018-01-01

In this study, we examined the removal of arsenite (As(III)) and arsenate (As(V)) by perilla leaf-derived biochars produced at 300 and 700 °C (referred as BC300 and BC700) in aqueous environments. Results revealed that the Langmuir isotherm model provided the best fit for As(III) and As(V) sorption, with the sorption affinity following the order: BC700-As(III) > BC700-As(V) > BC300-As(III) > BC300-As(V) (Q L  = 3.85-11.01 mg g -1 ). In general, As removal decreased (76-60%) with increasing pH from 7 to 10 except for the BC700-As(III) system, where notably higher As removal (88-90%) occurred at pH from 7 to 9. Surface functional moieties contributed to As sequestration by the biochars examined here. However, significantly higher surface area and aromaticity of BC700 favored a greater As removal compared to BC300, suggesting that surface complexation/precipitation dominated As removal by BC700. Arsenic K-edge X-ray absorption near edge structure (XANES) spectroscopy demonstrated that up to 64% of the added As(V) was reduced to As(III) in BC700- and BC300-As(V) sorption experiments, and in As(III) sorption experiments, partial oxidation of As(III) to As(V) occurred (37-39%). However, XANES spectroscopy was limited to precisely quantify As binding with sulfur species as As 2 S 3 -like phase. Both biochars efficiently removed As from natural As-contaminated groundwater (As: 23-190 μg L -1 ; n = 12) despite in the presence of co-occurring anions (e.g., CO 3 2- , PO 4 3- , SO 4 2- ) with the highest levels of As removal observed for BC700 (97-100%). Overall, this study highlights that perilla leaf biochars, notably BC700, possessed the greatest ability to remove As from solution and groundwater (drinking water). Significantly, the integrated spectroscopic techniques advanced our understanding to examine complex redox transformation of As(III)/As(V) with biochar, which are crucial to determine fate of As on biochar in aquatic environments. Copyright © 2017 Elsevier Ltd. All rights reserved.

Body mass index in ambulatory cerebral palsy patients.

PubMed

Feeley, Brian T; Gollapudi, Kiran; Otsuka, Norman Y

2007-05-01

Malnutrition is a common problem in children with cerebral palsy. Although malnutrition is often recognized in patients with severe cerebral palsy, it can be unrecognized in less severely affected patients. The consequences of malnutrition are serious, and include decreased muscle strength, poor immune status, and depressed cerebral functioning. Low body mass index has been used as a marker for malnutrition. The purpose of this study was to determine which patients in an ambulatory cerebral palsy patient population were at risk for low body mass index. A retrospective chart review was performed on 75 patients. Age, sex, height, weight, type of cerebral palsy, and functional status [gross motor functional classification system (GMFCS) level] was recorded from the chart. Descriptive statistics with bivariate and multivariate regression analyses were performed. Thirty-eight boys and 37 girls with an average age of 8.11 years were included in the study. Unique to our patient population, all cerebral palsy patients were independent ambulators. Patients with quadriplegic cerebral palsy had a significantly lower body mass index than those with diplegic and hemiplegic cerebral palsy. Patients with a GMFCS III had significantly lower body mass index than those with GMFCS I and II. When multivariate regression analysis to control for age and sex was performed, low body mass index remained associated with quadriplegic cerebral palsy and GMFCS III. Malnutrition is a common health problem in patients with cerebral palsy, leading to significant morbidity in multiple organ systems. We found that in an ambulatory cerebral palsy population, patients with lower functional status or quadriplegia had significantly lower body mass index, suggesting that even highly functioning ambulatory cerebral palsy patients are at risk for malnutrition.

Clinical interpretation of a masticatory normative indicator analysis of masticatory function in subjects with different occlusal and prosthodontic status.

PubMed

Witter, Dick J; Woda, Alain; Bronkhorst, Ewald M; Creugers, Nico H J

2013-05-01

To analyse the masticatory function of subjects characterised by different occlusal and prosthodontic status. Using Optosil(®) as a test food, the masticatory normative indicator (MNIOPT) was used to differentiate between sufficient ('normal') and impaired masticatory function. Outcomes of occlusal force and masticatory tests were aggregated from three earlier studies dealing with four denture groups and three natural dentition groups. The four denture groups had a complete removable dental prosthesis in the upper jaw, and displayed one of the four following lower jaw prosthodontic rehabilitations: (i) complete removable dental prosthesis on a low mandible; (ii) complete removable dental prosthesis on a higher mandible; (iii) overdenture on natural roots; and (iv) overdenture on dental implants. The three natural dentition groups were: (i) shortened dental arch; (ii) complete dentition in older participants, and (iii) complete dentition in younger participants. All participants were women. They performed the same tests twice, and outcomes were averaged. A MNIOPT value of 3.68 mm was determined from the participants with complete natural dentitions. Applying the MNIOPT to the participants in the denture groups pointed at a considerable chance for impaired masticatory function, except for participants in the overdenture -implants group. The four denture groups compensated for reduced masticatory efficiency by increased number of masticatory cycles and prolonged mastication time until 'swallowing'. Nevertheless, they also 'swallowed' larger particles compared to the complete dentition group. For a given patient or for a group of subjects with specific dental conditions, MNI enables to discriminate between a sufficient ('normal') and an impaired masticatory function. Copyright © 2013 Elsevier Ltd. All rights reserved.

CHEMICAL ENRICHMENT OF DAMPED Ly{alpha} SYSTEMS AS A DIRECT CONSTRAINT ON POPULATION III STAR FORMATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kulkarni, Girish; Hennawi, Joseph F.; Rollinde, Emmanuel

2013-08-01

Observations of damped Ly{alpha} absorbers (DLAs) can be used to measure gas-phase metallicities at large cosmological look-back times with high precision. Furthermore, relative abundances can still be measured accurately deep into the reionization epoch (z > 6) using transitions redward of Ly{alpha}, even though Gunn-Peterson absorption precludes measurement of neutral hydrogen. In this paper, we study the chemical evolution of DLAs using a model for the coupled evolution of galaxies and the intergalactic medium (IGM), which is constrained by a variety of observations. Our goal is to explore the influence of Population III stars on the abundance patterns of DLAsmore » to determine the degree to which abundance measurements can discriminate between different Population III stellar initial mass functions (IMFs). We include effects, such as inflows onto galaxies due to cosmological accretion and outflows from galaxies due to supernova feedback. A distinct feature of our model is that it self-consistently calculates the effect of Population III star formation on the reionization of an inhomogeneous IGM, thus allowing us to calculate the thermal evolution of the IGM and implement photoionization feedback on low-mass galaxy formation. We find that if the critical metallicity of Population III to II/I transition is {approx}< 10{sup -4} Z{sub Sun }, then the cosmic Population III star formation rate drops to zero for z < 8. Nevertheless, at high redshift (z {approx} 6), chemical signatures of Population III stars remain in low-mass galaxies (halo mass {approx}< 10{sup 9} M{sub Sun }). This is because photoionization feedback suppresses star formation in these galaxies until relatively low redshift (z {approx} 10), and the chemical record of their initial generation of Population III stars is retained. We model DLAs as these low-mass galaxies, and assign to them a mass-dependent H I absorption cross-section in order to predict the expected distribution of DLA abundance ratios. We find that these distributions are anchored toward abundance ratios set by Population II supernova yields, but they exhibit a tail which depends significantly on the Population III IMF for z > 5. Thus, a sample of DLA metallicity and relative abundance measurements at high redshift holds the promise to constrain Population III enrichment and the Population III IMF. We find that a sample of just 10 DLAs with relative abundances measured to an accuracy of 0.1 dex is sufficient to constrain the Population III IMF at 4{sigma}. These constraints may prove stronger than other probes of Population III enrichment, such as metal-poor stars and individual metal-poor DLAs. Our results provide a global picture of the thermal, ionization, and chemical evolution of the universe, and have the potential to rule out certain Population III scenarios.« less

Altered mitochondrial function and oxidative stress in leukocytes of anorexia nervosa patients.

PubMed

Victor, Victor M; Rovira-Llopis, Susana; Saiz-Alarcon, Vanessa; Sangüesa, Maria C; Rojo-Bofill, Luis; Bañuls, Celia; Falcón, Rosa; Castelló, Raquel; Rojo, Luis; Rocha, Milagros; Hernández-Mijares, Antonio

2014-01-01

Anorexia nervosa is a common illness among adolescents and is characterised by oxidative stress. The effects of anorexia on mitochondrial function and redox state in leukocytes from anorexic subjects were evaluated. A multi-centre, cross-sectional case-control study was performed. Our study population consisted of 20 anorexic patients and 20 age-matched controls, all of which were Caucasian women. Anthropometric and metabolic parameters were evaluated in the study population. To assess whether anorexia nervosa affects mitochondrial function and redox state in leukocytes of anorexic patients, we measured mitochondrial oxygen consumption, membrane potential, reactive oxygen species production, glutathione levels, mitochondrial mass, and complex I and III activity in polymorphonuclear cells. Mitochondrial function was impaired in the leukocytes of the anorexic patients. This was evident in a decrease in mitochondrial O2 consumption (P<0.05), mitochondrial membrane potential (P<0.01) and GSH levels (P<0.05), and an increase in ROS production (P<0.05) with respect to control subjects. Furthermore, a reduction of mitochondrial mass was detected in leukocytes of the anorexic patients (P<0.05), while the activity of mitochondrial complex I (P<0.001), but not that of complex III, was found to be inhibited in the same population. Oxidative stress is produced in the leukocytes of anorexic patients and is closely related to mitochondrial dysfunction. Our results lead us to propose that the oxidative stress that occurs in anorexia takes place at mitochondrial complex I. Future research concerning mitochondrial dysfunction and oxidative stress should aim to determine the physiological mechanism involved in this effect and the physiological impact of anorexia.

Effects of a novel immune modulation therapy in patients with advanced chronic heart failure: results of a randomized, controlled, phase II trial.

PubMed

Torre-Amione, Guillermo; Sestier, François; Radovancevic, Branislav; Young, James

2004-09-15

We sought to determine whether a novel, non-pharmacological form of immune modulation therapy (IMT), shown experimentally to reduce inflammatory and increase anti-inflammatory cytokines, improved outcomes in patients with advanced heart failure (HF). Immune activation contributes to the progression of HF, but treatments directed against inflammation have been largely unsuccessful. Seventy-five HF patients (New York Heart Association [NYHA] functional class III to IV) were randomized to receive either IMT (n = 38) or placebo (n = 37) in a double-blind trial for six months, with continuation of standard HF therapy. Patients were evaluated using the 6-min walk test, changes in NYHA functional class, cardiac function, and quality of life assessments, as well as occurrence of death and hospitalization. There was no between-group difference in 6-min walk test, but 15 IMT patients (compared with 9 placebo) improved NYHA functional classification by at least one class (p = 0.140). The Kaplan-Meier survival analysis showed that IMT significantly reduced the risk of death (p = 0.022) and hospitalization (p = 0.008). Analysis of a clinical composite score demonstrated a significant between-group difference (p = 0.006). There was no difference in left ventricular ejection fraction, but there was a trend toward improved quality of life (p = 0.110). These preliminary findings are consistent with the hypothesis that immune activation is important in the pathogenesis of HF and establish the basis for a phase III trial to define the benefit of IMT in chronic HF.

Chiral alkynylcarbinols from marine sponges: asymmetric synthesis and biological relevance.

PubMed

Listunov, Dymytrii; Maraval, Valérie; Chauvin, Remi; Génisson, Yves

2015-01-01

Covering: up to March 2014. Previous review on the topic: B. W. Gung, C. R. Chim., 2009, 12, 489-505. Chiral α-functional lipidic propargylic alcohols extracted from marine sponges, in particular of the pacific genus Petrosia, constitute a class of acetylenic natural products exhibiting remarkable in vitro biological activities, especially anti-tumoral cytotoxicity. These properties, associated to functionalities that are uncommon among natural products, have prompted recent projects on asymmetric total synthesis. On the basis of a three-sector structural typology, three main sub-types of secondary alkynylcarbinols (with either alkyl, alkenyl, or alkynyl as the second substituent) can be identified as the minimal pharmacophoric units. Selected natural products containing these functionalities have been targeted using previously known or on purpose-designed procedures, where the stereo-determining step can be: (i) a C-C bond forming reaction (e.g. the Zn-mediated addition of alkynyl nucleophiles to aldehydes in the presence of chiral aminoalcohols), (ii) a functional layout (e.g. the asymmetric organo- or metallo-catalytic reduction of ynones), or (iii) an enantiomeric resolution (e.g. a lipase-mediated kinetic resolution via acetylation). The promising medicinal importance of these targets is finally surveyed, and future investigation prospects are proposed, such as: (i) further total synthesis of known or future extraction products; (ii) the synthesis of non-natural analogues, with simpler lipophilic environments of the alkynylcarbinol-based pharmacophoric units; (iii) the variation and optimization of both the pharmacophoric units and their lipophilic environment; and (iv) investigations into the biological mode of action of these unique structures.

Integrated Computational and Experimental Protocol for Understanding Rh(III) Speciation in Hydrochloric and Nitric Acid Solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Samuels, Alex C.; Boele, Cherilynn A.; Bennett, Kevin T.

2014-12-01

A combined experimental and theoretical approach has investigated the complex speciation of Rh(III) in hydrochloric and nitric acid media, as a function of acid concentration. This has relevance to the separation and isolation of Rh(III) from dissolved spent nuclear fuel, which is an emergent and attractive alternative source of platinum group metals, relative to traditional mining efforts.

Thermodynamic study on the role of hydrogen during the MOVPE growth of group III nitrides

NASA Astrophysics Data System (ADS)

Koukitu, Akinori; Taki, Tetsuya; Takahashi, Naoyuki; Seki, Hisashi

1999-02-01

The role of hydrogen during the MOVPE growth of group III nitrides is investigated from a thermodynamic point of view. The effect of hydrogen is reported for the driving force for the deposition of binary nitrides as functions of growth temperature and V/III ratio. The effect of hydrogen for the InGaN growth is discussed for the vapor-solid relationship, the formation of compositional inhomogeneity and input partial pressure of the group III elements. The difference between the growth reaction of the indium containing nitrides and that of other III-V compounds is also discussed.

Potentiometry: A Chromium (III) -- EDTA Complex

ERIC Educational Resources Information Center

Hoppe, J. I.; Howell, P. J.

1975-01-01

Describes an experiment that involves the preparation of a chromium (III)-EDTA compound, a study of its infrared spectrum, and the potentiometric determination of two successive acid dissociation constants. (Author/GS)

Bioadsorption and bioaccumulation of chromium trivalent in Cr(III)-tolerant microalgae: a mechanisms for chromium resistance.

PubMed

Pereira, M; Bartolomé, M C; Sánchez-Fortún, S

2013-10-01

Anthropogenic activity constantly releases heavy metals into the environment. The heavy metal chromium has a wide industrial use and exists in two stable oxidation states: trivalent and hexavalent. While hexavalent chromium uptake in plant cells has been reported that an active process by carrying essential anions, the cation Cr(III) appears to be taken up inactively. Dictyosphaerium chlorelloides (Dc1M), an unicellular green alga is a well-studied cell biological model organism. The present study was carried out to investigate the toxic effect of chromium exposures on wild-type Cr(III)-sensitive (Dc1M(wt)) and Cr(III)-tolerant (Dc1M(Cr(III)R30)) strains of these green algae, and to determine the potential mechanism of chromium resistance. Using cell growth as endpoint to determine Cr(III)-sensitivity, the IC₅₀(₇₂) values obtained show significant differences of sensitivity between wild type and Cr(III)-tolerant cells. Scanning electron microscopy (SEM) showed significant morphological differences between both strains, such as decrease in cell size or reducing the coefficient of form; and transmission electron microscopy (TEM) revealed ultrastructural changes such as increased vacuolization and cell wall thickening in the Cr(III)-tolerant strain with respect to the wild-type strain. Energy dispersive X-ray analysis (SEM/XEDS) revealed that Cr(III)-tolerant D. chlorelloides cells are able to accumulate considerable amounts of chromium distributed in cell wall (bioadsorption) as well as in cytoplasm, vacuoles, and chloroplast (bio-accumulation). Morphological changes of Cr(III)-tolerant D. chlorelloides cells and the presence of these electron-dense bodies in their cell structures can be understood as a Cr(III) detoxification mechanism. Copyright © 2013 Elsevier Ltd. All rights reserved.

Determination of gallium at trace levels using a spectrofluorimetric method in synthetic U-Ga and Ga-As solutions.

PubMed

Kara, Derya; Fisher, Andrew; Foulkes, Mike; Hill, Steve J

2010-01-01

A simple, easy to use and selective spectrofluorimetric method for the determination of trace levels of gallium has been developed. A new Schiff base, N-o-vanillidine-2-amino-p-cresol (OVAC) was synthesized and its fluorescence activity with gallium investigated. Based on this chelation reaction, a spectrofluorimetric method has been developed for the determination of gallium in synthetically prepared Ga-U and Ga-As samples buffered at pH 4.0 using acetic acid-sodium acetate. The chelation reaction between Ga(III) and N-o-vanillidine-2-amino-p-cresol was very fast, requiring only 30min at room temperature to complex completely. The limit of detection (LOD) (3sigma) for Ga(III) was 7.17 nM (0.50 microgL(-1)), determined from the analysis of 11 different solutions of 20 microg L(-1) Ga(III). Copyright 2009 Elsevier B.V. All rights reserved.

Determination of Trace Amounts of Chromium(III) in Water Samples Using Online Flow Injection Catalytic Spectrophotometry

NASA Astrophysics Data System (ADS)

Zhao, Z. X.; Zhang, X. S.

2017-01-01

A new online flow injection spectrophotometric method for the determination of trivalent chromium was developed. This method is based on the property of trivalent chromium to be a catalyst for the oxidation of Indigo Carmine (IC) with potassium periodate and to lose its color in the presence of ethylenediaminetetraacetic acid and sodium tripolyphosphate. It was shown that Tween-20 serves as an additional accelerator of the catalytic oxidation. The linear dynamic range of the determination of Cr(III) was 1-40.0 μg/L, while the limit of detection was 0.05 μg/L. The correlation coefficient r was 0.998, while the relative standard deviation for 5 μg/L of the Cr(III) solution was 3.83%. The feasibility of this method was checked by its application to trivalent chromium determination in real water samples.

Rhodium(III)-Catalyzed Activation of C(sp3)-H Bonds and Subsequent Intermolecular Amidation at Room Temperature.

PubMed

Huang, Xiaolei; Wang, Yan; Lan, Jingbo; You, Jingsong

2015-08-03

Disclosed herein is a Rh(III)-catalyzed chelation-assisted activation of unreactive C(sp3)-H bonds, thus enabling an intermolecular amidation to provide a practical and step-economic route to 2-(pyridin-2-yl)ethanamine derivatives. Substrates with other N-donor groups are also compatible with the amidation. This protocol proceeds at room temperature, has a relatively broad functional-group tolerance and high selectivity, and demonstrates the potential of rhodium(III) in the promotive functionalization of unreactive C(sp3)-H bonds. A rhodacycle having a SbF6(-) counterion was identified as a plausible intermediate. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Repair-oriented classification of aortic insufficiency: impact on surgical techniques and clinical outcomes.

PubMed

Boodhwani, Munir; de Kerchove, Laurent; Glineur, David; Poncelet, Alain; Rubay, Jean; Astarci, Parla; Verhelst, Robert; Noirhomme, Philippe; El Khoury, Gébrine

2009-02-01

Valve repair for aortic insufficiency requires a tailored surgical approach determined by the leaflet and aortic disease. Over the past decade, we have developed a functional classification of AI, which guides repair strategy and can predict outcome. In this study, we analyze our experience with a systematic approach to aortic valve repair. From 1996 to 2007, 264 patients underwent elective aortic valve repair for aortic insufficiency (mean age - 54 +/- 16 years; 79% male). AV was tricuspid in 171 patients bicuspid in 90 and quadricuspid in 3. One hundred fifty three patients had type I dysfunction (aortic dilatation), 134 had type II (cusp prolapse), and 40 had type III (restrictive). Thirty six percent (96/264) of the patients had more than one identified mechanism. In-hospital mortality was 1.1% (3/264). Six patients experienced early repair failure; 3 underwent re-repair. Functional classification predicted the necessary repair techniques in 82-100% of patients, with adjunctive techniques being employed in up to 35% of patients. Mid-term follow up (median [interquartile range]: 47 [29-73] months) revealed a late mortality rate of 4.2% (11/261, 10 cardiac). Five year overall survival was 95 +/- 3%. Ten patients underwent aortic valve reoperation (1 re-repair). Freedoms from recurrent Al (>2+) and from AV reoperation at 5 years was 88 +/- 3% and 92 +/- 4% respectively and patients with type I (82 +/- 9%; 93 +/- 5%) or II (95 +/- 5%; 94 +/- 6%) had better outcomes compared to type III (76 +/- 17%; 84 +/- 13%). Aortic valve repair is an acceptable therapeutic option for patients with aortic insufficiency. This functional classification allows a systematic approach to the repair of Al and can help to predict the surgical techniques required as well as the durability of repair. Restrictive cusp motion (type III), due to fibrosis or calcification, is an important predictor for recurrent Al following AV repair.

Iron speciation in peats: Chemical and spectroscopic evidence for the co-occurrence of ferric and ferrous iron in organic complexes and mineral precipitates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhattacharyya, Amrita; Schmidt, Michael P.; Stavitski, Eli

The speciation of iron (Fe) in organic matter (OM)-rich environments under in situ variable redox conditions is largely unresolved. Peatlands provide a natural setting to study Fe–OM interactions. Utilizing chemical, spectroscopic and theoretical modeling approaches, we report the chemical forms, oxidation states and local coordination environment of naturally occurring Fe in the vertically redox-stratified Manning peatlands of western New York. In addition, we report dominant carbon, sulfur and nitrogen species that can potentially stabilize the various Fe species present in these peatlands. Our results provide clear direct and indirect evidence for the co-occurrence of ferrous (Fe 2+) and ferric (Femore » 3+) iron species in peats under both oxic and anoxic conditions. Iron is mostly present within the operationally defined organic and amorphous (i.e., short range ordered, SRO) fractions; ferric iron primarily as magnetically isolated paramagnetic Fe 3+ in Fe(III)-organic complexes, but also in mineral forms such as ferrihydrite; ferrous iron in tetrahedral coordination in Fe(II)-organic complexes with minor contribution from pyrite. All of the Fe species identified stabilize Fe(III) and/or Fe(II) in anoxic and oxic peats. Fundamental differences are also observed in the relative proportion of C, S and N functionalities of OM in oxic and anoxic peats. Aromatic C=C, ester, phenol and anomeric C (R-O-C-O-R), as well as thiol, sulfide and heterocyclic N functionalities are more prevalent in anoxic peats. Collectively, our experimental evidence suggests iron forms coordination complexes with O-, S- and N-containing functional groups of OM. We posit the co-occurrence of organic and mineral forms of Fe(II) and Fe(III) in both oxic and anoxic peat layers results from dynamic complexation and hydrolysis-precipitation reactions that occur under variable redox conditions. In conclusion, our findings aid in understanding the crucial role OM plays in determining Fe species in soils and sediments.« less